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A Study of the reactions of some nitrogen and phosphorus bases: (I) with triethylaluminum; (II) with chloramine

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Title:
A Study of the reactions of some nitrogen and phosphorus bases: (I) with triethylaluminum; (II) with chloramine
Creator:
Clemens, Donald Faull, 1929-
Publication Date:
Copyright Date:
1965
Language:
English
Physical Description:
viii, 144 l. : illus. ; 28 cm.

Subjects

Subjects / Keywords:
Aluminum ( jstor )
Atomic spectra ( jstor )
Atoms ( jstor )
Infrared spectrum ( jstor )
Magnetic resonance spectroscopy ( jstor )
Magnetic spectroscopy ( jstor )
Nitrogen ( jstor )
Nuclear magnetic resonance ( jstor )
Phosphorus ( jstor )
Protons ( jstor )
Chemistry thesis Ph. D
Chloramine ( lcsh )
Dissertations, Academic -- Chemistry -- UF
Triethylaluminum ( lcsh )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis - University of Florida.
Bibliography:
Bibliography: l. 141-143.
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Also available on World Wide Web
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Manuscript copy.
General Note:
Vita.

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University of Florida
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University of Florida
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Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
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ACH2402 ( NOTIS )

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A STUDY OF THE REACTIONS OF SOME
NITROGEN AND PHOSPHORUS BASES:

(I) WITH TRIETHYLALUMINUM;

(II) WITH CHLORAMINE














By
DONALD FAULL CLEMENS


A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY











UNIVERSITY OF FLORIDA
April, 1965













ACKNOWLEDGMENTS


The author wishes to recognize the friendly

assistance and moral support of his committee during the

course of this work.

The encouragement and enthusiasm provided by Pro-

fessor Harry H. Sisler, under whose direction this work was

carried out, has been most beneficial. Although busy with

administrative duties he has always had time to listen to

the author's problems with an attentive ear and has always

been helpful in obtaining the solutions to these problems.

Professor Wallace S. Brey has been of special

assistance in obtaining and interpreting nuclear magnetic

resonance spectra for this study.

The author is indebted to his colleagues, Mr. Stephen

E. Frazier and Mr. Robert L. McKenney, for the many chal-

lenging discussions and ideas shared during the course of

this work.

Acknowledgment is made to the donors of The Petroleum

Research Fund, administered by the American Chemical

Society, for support of this research.

Finally, the author wishes to express his gratitude

to his wife Kay, and his five children for their many

personal sacrifices. Without their encouragement this

work would not have been possible.
ii












TABLE OF CONTENTS

Page
ACKNOWLEDGME: TS . . . . . . . . . ii

LIST OF TABLES. . . . . . . . . ... iv

LIST OF FIGURES . . . . . . . . . v

PART I. A STUDY OF THE SYNTHESIS OF SOME ALUMINUM
DERIVATIVES OF PHOSPHORUS AND NITROGEN

INTRODUCTION .. . . . ....... 1

Historical Background . . . . . . 2

EXPERIMENTAL. . . . . . .. . . . . 6

DISCUSSION AND CONCLUSIONS. .. . . . . .. 68

SUMMARY . . . . . . . . . . . 87

PART II. A STUDY OF THE CHLORAMINATION OF
SOME I-INOPHOSPHINE DERIVATIVES

INTRODUCTION. . . . . . . . ... . 89

Historical Background. . . . . . . .. 90

EXPERIMENTAL. . . . . . . . ... .. . 95

DISCUSSION AND CONCLUSIONS . ........... 132

SUMMARY . . . . . . . . . . . 138

BIBLIOGRAPHY. .. . . . . . .. . 141

BIOGRAPHICAL SKETCH. . . . . . . . .. 144


iii












LIST OF TABLES


Table Page

1. Infrared Absorption in Cm.-1(Part I) .... 9

2. Infrared Absorption Assignments . . ... 14

3. Nuclear Magnetic Resonance Data (Part I) . 64

4. Infrared Absorption in Cm.-1 (Part II) . . 128

5. Nuclear Magnetic Resonance Data (Part II). 130
































o . .'
^. \./ . .








.-J






\ -- 7 \ \ j

.. / )


>3


--



2 2<


Ss A -* / *


i


~i, ~e


s w e e"^ ^ ^A- ** * *







Figure Page
17. (1H) Nuclear magnetic resonance spectrum of
(C2H5)2NP(C6H5)2A(C2H52H . . . . 40
18. Infrared spectrum of (CH )2PP(CH3)2.2Al(C2H5)3 43
19. Infrared spectrum of (C)2PP(CH)2. . . 44
20. ( H) Nuclear magnetic resonance spectrum of
(CH)2?P(CH )22A1(C2H . . . . .. 45
21. Infrared spectrum of
(C6H5)2PP(C H5)2A(C2H5)3 . . . . 47
22. Infrared spectrum of (C H5)2PP(C6H5)2. . 48
23. ( H) Nuclear magnetic resonance spectrum of
(C6H5)2PP(C6H5)2Al(C 25)3 . . . ... 50
24. Infrared spectrum of
C2 5N[P(C6H5)22A(C25 . . . . . 52
25. Infrared spectrum of C2H5N[P(C6H5)2]2. . .. 53
26. ( H) Nuclear magnetic resonance spectrum of
C2H5[P(C6H )232-AI(C25)3. . . . . . 54
27. Infrared spectrum of CH3N[P(C6H5)2]2'Al(C2H5)3 57
28. Infrared spectrum of CH3N[P(C6H5)2]2 . . 58
29. ( H) Nuclear magnetic resonance spectrum of
CH3 N[P(C6H5)2]2Al(C2H5)3 . . . . 59
30. Infrared spectrum of [(C2H5)2AlNCP(C6H5)212]2. 61
31. Infrared spectrum of HN[P(C6H5)2]2 . . . 62
32. Infrared spectrum of C2H NHP(C4H9)2 ... . 97
33. ( H) Nuclear magnetic resonance spectrum of
C2 H5HP(C4H9)2 . . . . . . . 98
34. Infrared spectrum of C2H5N[P(C 6H)2]2. . 100
35. ( H) Nuclear magnetic resonance spectrum of
C2H N[P(C 5)2 2 . . . . . . . . 101









Figure

36. Infrared spectrum of CH-N[P(C65)2]2 ..
37. (1H) Nuclear magnetic resonance spectrum of
CH3N[ (C6H5)2]2 . . . . . . .

58. Infrared spectrum of HN[P(CH5)2]2 . . .

39. The chloramine generator . . . . . .
40. Infrared spectrum of [(NH2)f(CH3)2NJP(CH )2]Cl

41. (1 ) Nuclear magnetic resonance spectrum of
[(H:2){ (CH )2N}P(CH3)2]Cl. . . . . .
42. (1H) Nuclear magnetic resonance spectrum of
(CH3)2NP(CH3)2 . . . . . . . .

43. Infrared spectrum of [(NH2)(C2H5NH)P(C4H9)2]C1

44. (1H) Nuclear magnetic resonance spectrum of
[(I.2)(C2H5NH)P(CH9)2]C1 . . . . .
45. Infrared spectrum of .
NH


?(C6H5)2
C2H5N ClH

NHI
I-: l2


46.


(1H) Nuclear magnetic resonance spectrum of
2- 'NT 2



(C6H5)2
NH2


Page

103

104

106

108

110

111

112

115

116

118


47. Infrared spectrum of


/P(C6H5)2
CH3 N
P(C6H5)2
I2
vii


. 121


Cl


. 119








Figure
48. (1H) Nuclear magnetic resonance spectrum of


P(cH,5)2


NE2
(CH
y6 5)2
2m


Cl . . . . . . 123


49. Infrared spectrum of
[(CH ) P(:TH:)rTP(Nm )(C6H5)2]lECcl. .
50. Infrared spectrum of
C(C6^5)2P("H2)P(I2)(C5)2]Cl. . . .
51. (1H) Nuclear magnetic resonance spectrum of
[(C6H5)2(NH2)(NH2)(C65)2]C . . .


viii


Page


S125


126

127












PART I. A STUDY OF THE SYNTHESIS OF SOME ALUMINUM
DERIVATIVES OF PHOSPHORUS AND NITROGEN


INTRODUCTION


Recent studies in this laboratory of the reactions

of triethylaluminum and ethylaluminum chlorides with

hydrazines have shown that if one or more of the groups

bonded to a nitrogen atom is a hydrogen atom, hydrocarbon

elimination takes place. If there is no hydrogen available

on the nitrogen atom the reaction proceeds to form a

molecular addition product. Tetramethylhydrazine reacts

with alkylaluminum compounds to form adducts which have

been postulated to contain pentacoordinate aluminum (1,2).

The existence of pentacoordinate aluminum has been proved

by the reactions of aluminum hydrides with two moles of

amine to form 1:2 complexes (3,4,5). It was thought that

the reactions of triethylaluminum with aminophosphines

and biphosphines might be very similar to its reactions

with hydrazines. An aminophosphine would provide several

possibilities for reaction: the aluminum atom could

become attached to the nitrogen atom, to the phosphorus

atom, or to both atoms. If both the nitrogen and

phosphorus atoms function as electron donor centers it







2

might be possible to attach two molecules of an alkyl-

aluminum compound to one molecule of the aminophosphine.

This study was conducted to determine how triethyl-

aluminum would interact with molecules containing more

than one basic center, to determine the nature of the

reaction products and to examine the possibility of the

existence of pentacoordinate aluminum in these compounds.


Historical Background

The literature contains many references to aluminum-

hydrogen or aluminum-carbon compounds reacting with

nitrogen-containing electron donor species. With the

exception of two arylaluminum compounds reported in 1930

(6), all such references appeared after the exploratory

work of Davidson and Brown in 1942 (7). Davidson and

Brown synthesized alkylaluminum derivatives of trimethyl-

amine, trimethylphosphine, dimethylether, and dimethyl-

sulfide.

The large number of reports concerning aluminum-

nitrogen chemistry is in sharp contrast to the relatively

small number of papers dealing with the reactions of

aluminum hydride or aluminum alkyls with phosphorus-

containing bases. The aluminum-phosphorus compounds

reported as products of such reactions can be placed in

four categories. In each case an example is given.









1. Molecular addition compounds of trialkylphosphines
with aluminum hydride or aluminum alkyls (7,8).
AlI CH)6 + 2(CHE)3P 2(CH3)3P*Al(CH3 )

2. Alkylphosphinoaluminum hydrides (9,10).
3H2AlCl + 3LiP(C2H5)2 [H2AlP(C2H5)2]3 + 3LiCl

3. Alkyl- and arylphosphinoaluminumalkyls or alkyl-
aluminum phosphides (11).
(C2H5) 2A1C + C A(C2 )2 (C2(5)2Al?(C 25)2 + CH3Cl

4. Molecular addition compounds of biphosphines with

aluminum alkyls (12).
2(C -5)2PP(c 5)2 + Al2(C2:5)6

2(65) 2P?(C 5)2.Al(C 25) 3

The interaction of polynuclear electron-donor mole-
cules with aluminum alkyls was until recently unexplored.
Within the last four years, however, a number of papers
concerning interactions of aluminum alkyls with polynuclear
bases have appeared.
Paterson and Onyszchuk synthesized an extremely
shock sensitive compound, with the formula
(CH )2AlNHXHAl(CH3)2, by allowing trimethylaluminum to re-
act with hydrazine (13).
Al2(CH3)6 + N2H4 2CH + (CH3)2AI HNTHAI(CH )2









The interactions of methylhydrazines with aluminum

alkylshave been studied by several research groups. Fetter

and Bartocha (2) have synthesized a number of compounds by

the reactions of trimethylaluminum and trimethylaluminum-

trimethylamine with methylhydrazine, 1,2-dimethylhydrazine,

1,1-dimethylhydrazine, trimethylhydrazine, and tetramethyl-

hydrazine.

(CH3)3Al.N(CH3)3 + HN(CH3)N(CH )2 (CH )3A1.NH(CH )N(CH3)2

+ N(CH 3)

A1(CH)6 + 2H2ITN(CH)2 [(CH )2A1NiN(CH )2 2 + 2CH4

These investigations were extended in our laboratories by

a study of the interaction of triethylaluminum with 1,1-

dimethylhydrazine (14) and by the interaction of 1,1-di-

methylhydrazine and tetramethylhydrazine with ethyl and

ethylchloroaluminum compounds (1). The product of the re-

action of ethylaluminum dichloride with trimethylhydrazine

was also isolated and characterized

Al2(C2H5)4C1 2 + 2H NN(CH3)2 [C2H5AlClNHN(CH )2]2
+ 2C2H6

Al2(C2H5)6 + 2(CH3)2NN(CH )2 2 2(CH3)2NN(CH)2 Al(C2H5)3

.It has been shown that trimethyl and triethylalumi-

num react with tetramethylethylenediamine, tetraethylethyl-

enediamine, and tetramethylmethylenediamine to form complexes








which contain two moles of aluminum per mole of diamine

(15,16).
A12(C2 5)6 + (CH 3)N(CH2)2(CH2 -

(CH3)2N(CH2)2N(CH3)2*2Al(C2H5)3

BrUser, Thiele, and MIller have synthesized 1:1
addition complexes of a,a'-dipyridyl and 1,10-phenan-
throlene with trimethyl- and triethylaluminum (15). They
did not claim that the aluminum is pentacoordinate in these
complexes. However, Dr. Thiele has indicated this in a
private communication with the author.


Al2(C2H5)6 + 2 / ----/ 2( Al(C2H5)3


The interaction of tetramethyltetrazene with tri-
methylaluminum has been shown to yield the 1:1 adduct,

(CH)2 NN = NN(CH3)2-Al(C2H5)3, which decomposes unless it
is stored at temperatures of -100 or lower (17).
In the previous discussion concerning aluminum
phosphorus compounds it was noted that tetraphenylbi-
phosphine reacts with triethylaluminum to form the 1:1
adduct (12). This is the only literature reference to this
type reaction.











EXPERIMENTAL


The maniDulation of reagents

All organo-aluminum compounds were handled either

in a dry box (D. L. Herring Dri-Lab and Dri-Train combi-

nation), in an atmosphere of nitrogen, or in the glass

vacuum line shown in Figure 1. Oxygen and moisture were

rigorously excluded from all operations. Before reaction,

all materials were degassed by freezing with liquid

nitrogen, evacuating the reaction flask, closing the

manifold stopcock, and allowing the material to warm to

ambient temperature, this operation being carried out

three times. In those reactions in which ethane was a

product the liberated ethane was collected, purified,

identified by its vapor pressure at -126.35 and -111.60

(literature (18) 55mm; 178mm), and its volume was measured.

Materials

Solvents were dried by distillation over calcium

hydride and then stored over the same reagent. Triethyl-

aluminum obtained from the Ethyl Corporation was

fractionally distilled and the fraction boiling at 560

(0.5mm) was used. The preparation of the aminophosphines

and the biphosphines used in this work is discussed in

Part II.

















A


-S.-
A^-~


~I ij



i
*:...^_
~^.j~


\IZZZ


~-~i~7~------------~--~ r-


r


i
i~T~-ji V


G-->
i

~











Analyses

Elemental analyses were done by the Schwarzkopf

Microanalytical Laboratory. Melting points were obtained

in sealed capillary tubes in a Thomas-Hoover capillary

melting point apparatus and are uncorrected.

Molecular weights were determined cryoscopically in

benzene. An attempt to use a vapor-pressure osmometer was

unsuccessful because the compounds decomposed in the short

time they were in the instrument. A standard freezing

point apparatus was modified to provide a slow nitrogen

flush so that contact of the solution with the atmosphere

could be minimized. The molecular weights reported are not

very accurate. The values are generally low indicating

that the compounds may have partially hydrolyzed despite

all the precautions taken to exclude moisture from the

cryoscopic systems.

Infrared spectra

The infrared spectra were recorded on a Perkin-Elmer

Model 137 spectrometer using sodium chloride optics. The

spectra of the solids were obtained from Nujol mulls. In

all cases the samples were prepared in the dry box and

stored under nitrogen until being placed in the instrument.

A summary of the infrared data is found in Table 1.








TALE 1
INFRARED ABSORPTION IN CM.-1
(PART I)*


[C3H7N A1(C2H5)2 P(C6H5)2]3

nujol






C3 7NHP(C6H5)2
neat


A12(C2H5)6
neat


C4H9NHP(C6H5)2A1l(C2H5)3
neat


3080(sh,s), 2960(vs), 1950(vw),
1890(vw), 1810(vw), 1580(vw),
1470(sh,s), 1460(vs), 1430(s),
1400(m), 1380(vs), 1510(w),
1220(w), 1190(w), 1170(m),
1120(s), 1100(s), 1070(w),
1020(m), 1000(vs), 978(vs),
953(s) 933(m), 896(vs),
843(vs), 743(sh,vs), 740(vs),
693(vs).
3420(m), 3120(s), 3020(s),
1969(w), 1890(w), 1820(w),
1660(w), 1590(m), 1490(s),
1470(s), 1440(vs), 1400(sh,s),
1380(s), 1370(s), 1330(m),
1310(m), 1270(w), 1170(vs),
1140(vs), 1100(vs), 1070(m),
1030(s), 1010(sh,vs), 998(vs),
916(w), 868(s), 800(m,b),
749(sh,vs), 742(vs), 696(vs,b).
2940(vs), 2150(vw), 1790(w,b),
1460(vs), 1410(vs), 1390(sh,vs),
1380(sh,s), 1330(sh,m,b),
1230(s), 1210(sh,s), 1190(s),
1100(m), 1060(m), 988(vs,b),
955(vs), 901(s), 869(m,b),
746(s,b).
3460(m), 3130(s), 2970(vs),
2840(sh,s), 1970(vw), 1900(vw),
1820(vw), 1660(vw), 1590(w),
1570(sh,vw), 1490(s), 1470(s),
1440(vs), 1410(s), 1570(vs),
1310(w), 1220(vs), 1200(vs),
1190(sh,s), 1160(sh w),
1120(sh,w), 1100(vs 1070(m),
1040(sh,m), 1030(s), 1010(vs),
998(vs), 990(sh,vs,b), 951(vs),
922(m), 855(sh w,b), 840(m,b),
778(w) 746(vs), 752(vs),
694(vs).


s, Strong; m, medium; w, weak; sh, shoulder; d, doublet; b,
broad.









Table 1 Cont'd.


CI H9HP(C6 5 )2
neat







C4H9N[A1(C2H 5) ]P(C6H5)2
nujol


(CEH)2NP(CH)2-Al(C2H5)
neat




(CH3)2NP(CH3)2
neat


(C2H5)2NP(C6H5)2Al(C2H5)2H
neat


3420(w), 3110(s), 3010(vs),
2920(sh,s), 1950(w), 1880(w),
1810(w), 1660(w), 150S(m),
1570(sh,w), 1470(vs),
1460(sh,s), 1450(vs),
1590(sh,m), 1360(vs), 1520(w),
1500(m), 1270(m), 1220(vs),
1200(sh,s), 1180(sh,m),
1150(w), 1090(s), 1070(m),
1030(s), 980(vs,b), 916(w,b),
837(s,b), 746(sh,vs,b),
732(vs), 695(vs).
3110(sh,s), 2950(vs), 1970(vw),
1900(vw), 1820(vw), 1580(vw),
1460(vs), 1440(vs), 1410(m),
1390(sh,s), 1370(vs), 1360(s),
1310(w), 1220(m), 1210(sh,m),
1180(s), 1160(sh,m), 1090(s),
1080(sh,w), 1040(s), 1050(m),
982(vs), 959(s), 924(m),
855(vs), 847(sh,vs), 975(s),
739(vs), 708(m), 696(vs).
2940(vs), 2840(s), 1470(sh,m),
1460(s), 1420(s), 1410(s),
1370(m), 1300(s), 1280(s),
1270(m), 1230(s), 1180(vs),
1170(sh,m), 1140(vw), 1120(s),
1060(s), 1040(s), 1020(m),
980(vs), 945(vs), 902(vs),
851(s), 826(w), 745(w), 708(s,b).
3030(vs), 2960(vs), 2900(sh,vs),
2840(vs), 1470(sh,s), 1450(s),
1430(s), 1420(sh,m), 1290(s),
1270(s), 1190(vs), 1140(m),
1100(vw), 1060(s), 971(vs),
936(vs), 889(vs), 845(s),
811(m), 692(s).
3130(s), 2870(vs), 1970(w),
1890(w), 1820(w), 1770(vw),
1660(w), 1590(m), 1490(s),
1470(vs), 1410(s), 1380(vs),
1350(m), 1510(sh,m), 1290(s),
1230(m), 1200(vs), 1180(vs),
1100(vs), 1070(s), 1060(s),
1030(vs), 1000(s), 980(sh,s),
950(sh,s), 939(s), 926(s),
849(w), 794(s), 746(vs,b),
696(vs,b).







Table 1 Cont'd.


neat


(CH3)2PP(CH 3)22A1(C2H5)3
neat


(CH3)2PP(CH3)2
neat


(C6H )2PP(C6H5)2"Al(C2H5)3
nujol


(C6H5)2PP(C6H5)2
nujol





C2H5N[P(C6H5)2]2*AI(C2H )3
nujol


3100(s), 2990(vs), 2900(sh,s),
1950(w), 1880(w), 1810(w),
1760(vw), 1650(w), 1580(m),
1470(vs), 1460(s), 1430(vs),
1570(vs), 1340(m), 1520(sh,m),
1300(sh,m), 1290(s), 1190(sh,vs),
1180(vs), 1160(sh,m), 1090(vs),
1070(s), 1060(sh,s), 1020(vs),
998(s), 923(vs), 849(w), 790(s),
744(vs), 696(vs,b).
2910(vs), 1450(vs), 1410(vs),
1360(m), 1280(m), 1220(m),
1170(m), 980(vs,b), 943(vs),
909(sh,s,b), 889(sh,vs), 881(vs),
821(w,b), 754(m,b), 699(sh,w,b),
676(s,b).
3020(s), 2940(s), 2860(m),
1430(vs), 1290(s), 946(vs),
887(vs), 871(vs), 815(w), 708(vs).
3110(sh,s), 2870(vs), 2840(sh,s),
1970(w), 1900(w), 1820(w),
1660(w), 1580(m), 1470(sh,s),
1460(vs), 1430(vs), 1400(m),
1370(s), 1330(m), 1310(m),
1270(w), 1220(w), 1170(d,vs),
1110(s), 1090(vs), 1070(m),
1020(m), 998(s), 982(s), 945(m),
924(shm), 916(m), 844(vw,b),
742(vs), 718(s), 692(vs,b).
3130(sh,s), 2980(vs), 1960(vw),
1890(vw), 1820(vw), 1660(vw),
1580(w), 1560(w), 1470(vs),
1430(vs), 1580(s), 1320(w),
1300(m), 1200(sh,m), 1180(vs),
1160(m), 1120(m), 1110(s),
1090(s), 1070(s), 1030(m),
1000(s), 948(w,b), 922(w),
984(w,b), 971(s) 970(vs),
715(s), 693(vs,b).
3110(sh,s), 2960(vs), 2840(sh,s),
1970(vw), 1900(vw), 1820(vw),
1660(vw), 1590(vw), 1470(sh,s),
1460(vs), 1450(vs), 1400(m),
1380(s), 1310(m), 1230(w),
1180(m), 1150(s), 1100(s),
1090(s), 1060(s), 1030(m),
980(m,b), 948(m), 921(dm),
884(s,b), 974(s), 972(sh,s),
743(vs), 700(vs,b).








Table 1 Cont'd.


C2H5N [P(C6H5)2]2
nujol





CH3N[P(C6H5 )2]2Al(C2 5)3
nujol


CH N[P(C6H5)232
nujol





[(C2H )2AIN[P(C6H5)2]2]2
nujol


nujol


3110(sh,m), 2960(vs),
2900(sh,vs), 1970(vw), 1890(vw),
1820(..), 1590(w), 1460(s),
14$0(s) 1370(s), 1300(w),
1180(vw5, 1150(m), 1090(s),
1060(s), 1030(m), 998(w),
966(w), 924(m), 879(s), 854(w),
766(m), 749(s), 742(s),
738(sh,s), 695(b,s).
3120(sh,s), 2960(vs), 1970(w),
1890(w), 1820(w), 1590(w),
1480(s), 1460(s), 1430(vs),
1400(m), 1370(m), 1300(w),
1220(w) 1180(m), 1160(sh,w),
1100(vs), 1080(vs), 1070(s),
1030(w), 995(sh,m), 987(m),
969(m) 948(m), 916(w,b),
866(vs 747(vs), 698(vs).
3110(sh,vs), 2990(vs), 1960(vw),
1890(vw), 1820(vw), 1650(vw),
1580(m), 1470(vs), 1450(vs),
1420(sh,m), 1380(s), 1310(m),
1270(m), 1170(m), 1160(sh,m),
1090(vs), 1070(vs), 1020(m),
998(m), 966(vw), 917(d,w),
851(vs), 743(vs), 695(vs).
3110(shm), 2990(vs), 2900(sh,vs),
1970(vw, 1900(vw), 1820(vw),
1590(w), 1470(sh,m), 1460(vs),
1440(s), 1580(s), 1310(vw),
1250(w), 1180(w,b), 1160(w),
1100(s), 1070(w), 1030(w),
1000(m), 988(sh,w), 964(w),
924(m), 901(vs), 810(s), 792(vs),
752(sh,m), 741(vs), 704(sh,s),
694(vs).
3250(m), 3080(sh,m), 2960(vs),
2880(sh s), 1960(vw), 1890(vw),
1810(vw), 1480(sh,s), 1460(s),
1450(s), 1380(s), 1300(vw),
1270(w), 1250(m), 1160(vw,b),
1100(s), 1070(sh,w), 1020(m),
997(w) 916(sh,m), 905(sh,s),
897(vs 794(m), 749(s),
736(vs), 692(vs,b).









Nuclear magnetic resonance soectra

Nuclear magnetic resonance spectra were obtained

using a Varian high resolution spectrometer, Model V-4300-2,

equipped with field homogeneity control, magnet insulation,

and field stabilizer.

The shift values were obtained by sweeping through

the field slowly and interchanging a reference sample and

the sample being studied. In this work acetaldehyde was

used as the reference sample. The method produces the

sample peaks and the acetaldehyde peaks on the same

spectrum and from this the chemical shifts may be calcu-

lated in approximate 7 values. The shift of the phenyl

protons is measured from the highest peak. Phosphoric

acid (85 per cent) was used as an external standard for

measuring the 31P chemical shifts. The H spectra were

determined at 56.4 Mc; the 1P spectra, at 19.3 Mc. A

summary of the nuclear magnetic resonance data is found in

Table 2.

The interaction of isooropylaminodiohenylphosohine with
triethylaluminum

6(C )2CHHP(C6: 5)2 + 3A12(C2H )6

2[(CH )2CHNAl(C2H )2 P(C65)2 + 6C2H6

In a typical experiment a 1.66 gram (0.0146 mole)

sample of triethylaluminum was placed in a 100 ml, 2 neck

reaction flask containing a teflon coated magnetic stirring









TA3BL 2

ISPRARIED ABSORPTION ASSIG:IENTS


Ground

KE2




Phenyl

CE3

CHI'

P-H

Phenyl

Al-H

Phenyl

NH2
P-phenyl

CH2

C-CH

C-(CH
C-CI

C-CH

C-(CH-)

P-CH.

(CH )INP
CN


-1
Ran=e in cm.
Stretching absorptions (2 bands) 3500-5500 (m)

Stretching absorptions (1 band) 3500-3300 (m)

Stretching absorptions (1 band) 3400-3300 (m)

C-H stretching absorption near 3030 (m-w)

C-H stretching absorption 2962 and 2872 (s)

C-H stretching absorption 2962 and 2853 (s)

Phosphorus-hydrogen bond 2440-2350 (m)

C-H stretching absorption 2000-1660 (w)

Aluminum-hydrogen bond 1790-1720 (m)

C=C in-plane vibrations 1600-1450 (m)

NH deformation 1650-1590 (m)

Phosphorus-carbon bond 1450-1435 (m)

CH deformation 1465 (m)

CH deformation 1450 (m)

CE deformation 1395-1385 (m)

CH deformation 1385-1380 (s)

CH deformation 1370-1365 (s)

CH deformation 1365 (s)

Phosphorus-carbon bond 1320-1280 (m)

Nitrogen-phosphorus bond 1316-1282 (m)

CN vibrations in aliphatic amines 1220-1020 (m)


(C2 5 2 N Nitrogen-phosphorus bond
2--5)2 LD -


1210 (m)









Table 2 Cc
Grouo




(C2H 5)NP

P-phenyl

PN

CH


nt 'd.


Nitrogenphosphorus bond

Nitrogen-phosphorus bond

Nitrogen-phosphorus bond

Phosphorus-carbon bond

PN stretching absorption

Out-of-plane deformation (mono-
substituted benzene)


-l


-1
Range in cm.

1190 (s)

1175 (m)

1064- (s)

1005- 995 (m)

740- 700 (s)


710- 690 (s)


All assignments except the PN assignments are taken
from Bellamy (22).










bar. Three and fifty-four hundredths grams (0.0146 mole)

of isopropylaminodiphenylphosphine was placed in a tipping

tube and attached to the reaction flask. A vacuum stop-

cock was fitted into the other neck of the reaction flask

and the entire apparatus was attached to the vacuum line.

After degassing the reactants the isopropylaminodiphenyl-

phosphine was added to the reaction flask which was cooled

with liquid nitrogen. The reaction flask was allowed to

warm slowly to room temperature during which time a gas

was slowly evolved. The reaction flask was then heated

for 40 hours at 50-550 to insure completion of the re-

action. Fractional condensation yielded 0.0127 mole of

ethane. The apparatus was then transferred to the dry box

and the white solid material was recrystallized from hot

hexane. This material heated at 1890 with decomposition.

The yield based on ethane elimination was 87 per cent.

The infrared spectrum, Figure 2, of the solid product

shows a strong peak at 1120 cm.-I which is associated with

a tetracoordinate phosphorus atom having a P-phenyl bond

(19). For comparison, Figures 3 and 4 show the infrared

spectra of isopropylaminodiphenylphosphine and triethyl-

aluminum, respectively.

Anal. Calcd. for [(CH3)2CHN Al(C2H5)2P(C6H5 )2]3

C, 69.71; H, 8.31; N, 4.28; P, 9.46; mol. wt., 982. Found:

C, 69.50; H, 8.07; N, 4.49; P, 9.18; mol. wt., 983.







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The proton nuclear magnetic resonance spectrum,

Figure 5, is in accord with the formula but can not be used

to determine the polymeric nature of the material. This

spectrum was obtained from a sample of material dissolved

in benzene so the chemical shift value of the phenyl group

was not obtained. The peak labeled A is difficult to see

at this sweep rate; however, with a slow sweep rate and

high resolution the peak is plainly a heptet. This is

expected for the CH peak because the proton is coupled

with the protons of the two adjacent methyl groups. The

peak labeled B arises from the various methyl groups. The

methyls of the ethyl groups form a triplet because the

methyl protons are coupled with the methylene protons.

This-triplet has a doublet superimposed on it by the iso-

propyl methyl protons. This doublet arises from the methyl

protons coupling with the single proton on the adjacent

carbon atom. The C peak is an unsymmetrical quartet

brought about by the methylene protons of the ethyl group

coupling with the methyl protons.

The interaction of tertiarybutylaminodiDhenylDhosphine with
triethylaluminum

2(CH3)CNHP(C6H5)2 + A12(C2 5)

2(CH )3CNHP(C6H5)2.Al(C2H 5)

By the vacuum method outlined above 5.06 grams

(0.0197 mole) of tertiarybutylaminodiphenylphosphine was











ci 21

U>






OR
cN
in










oj
o






0













4-2
I





















CT )

o
tH
aP









combined with 2.24 grams (0.0190 mole) of triethylaluminum

using 10 ml of toluene as the solvent. The aminophosphine

was slowly added to the reaction flask which was cooled by

a dry ice-acetone bath.

The reaction mixture was stirred at -780 for an

hour and then allowed to warm to room temperature and

stirred for an additional hour. The solvent was then re-

moved under vacuum and the reaction product was transferred

to the dry box. Heating the reaction product above room

temperature caused immediate evolution of ethane.

The infrared spectrum, Figure 6, of the molecular

addition product clearly shows the NH stretching absorption
-! -l
at 3460 cm.- The peak at 1120 cm. associated with

tetracoordinate phosphorus having a P-phenyl bond is

missing from this spectrum. Figure 7 shows, for comparison,

the infrared spectrum of the starting material tertiary-

butylaminodiphenylphosphine.

Anal. Calcd. for (CH3)3CNHP(C6H5)2-Al(C2H5 )3

C, 71.13; H, 9.50; N, 3.77; P, 8.34; Al, 7.76; mol. wt.,

371. Found: C, 71.16; H, 9.60; N, 3.79; P, 8.29; Al,

7.21; mol. wt., 412.

The proton nuclear magnetic resonance spectrum of

this compound, Figure 8, was obtained from a pure sample

sealed in a glass tube. The peak labeled A is attributed

to the phenyl protons. Peak B arises from the NH proton.
















O

co






O
O




O
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0









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0
0
10


0
0
0
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0

0:
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- : .. _ -- -- -











t- --.: ..... .-~-(-c ... ,-
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Peak C is attributed to both the tertiarybutyl methyl

protons and to the methyl protons of the ethyl groups.

Thus, peak C results from the superposition of the singlet

peak from the tertiarybutyl methyl protons and the triplet

peak from the ethyl methyl protons. Peak D is the quartet

from the methylene protons coupling with the methyl protons.

The pyrolysis of (CH)3C.:NP(C6H )2"Al(C2H-)>

(CH ) CNHP(C6HC )*Al ) (CH ) CN[Al(C2 5)2]P( H)2

+ C2H6

A 5.26 gram (0.014 mole) sample of the adduct of

aluminum triethyl and t-butylaminodiphenylphosphine was

placed in a 25 ml reaction flask containing a magnetic

stirring bar. The flask was fitted with a vacuum stopcock,

attached to the vacuum line, and warmed (60-800) for 18

hours. The total amount of ethane evolved was 0.0136 mole

or 96 per cent of theory based on the above equation. The

light brown solid reaction product was transferred to the

dry box and recrystallized twice from benzene to yield a

white crystalline solid melting at 166-1670 with gas

evolution.

The infrared spectrum of this product, Figure 9,

does not show the tetracoordinate phosphorus peak at

1120 cm.-1. (The compound [(CH3)2CHN Al(C2H5)25P(C6H5)2]3

does show the peak at 1120 cm.-1.)

Anal. Calcd. for (CH3)3 CT[Al(C2H5)2]P(C6H )2:

C, 70.35; H, 8.56; N, 4.10; P, 9.07; Al, 7.90; mol. wt.,









:JZ- jL..-j-7FL zjn-ij. -2-.i
---_ . -

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r--


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-- -!----- 1--1 --
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I-

C
c"



r"





9-


c





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-: ::". :: ::: : L-; I : ;I V;-
1- ^ ^...I. ^^^^-j.-.r. : :
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4: : y.---1 --4- __:
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O I


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. .










541. Found: C, 70.25; H, 8.58; N, 4.24; P, 8.89; Al,

7.86; mol. wt., 320.

The proton nuclear magnetic reasonance spectrum,

Figure 10, was determined from a sample dissolved in

deuterated chloroform and sealed in a glass tube. Peaks A

and A' are assigned to the phenyl protons. The ortho-

protons of the benzene ring are sometimes shifted down

field when the aromatic ring is attached to various sub-

stituents. Therefore, these two peaks don't necessarily

mean that there are two types of phenyl groups present.

Peak B is attributed to all the methyl protons. This peak

is seen to result from the superposition of the singlet

peak from the tertiarybutyl methyl protons and the triplet

from the ethyl methyl protons. Peak C is a quartet arising

from the methylene protons of the ethyl groups.

The interaction of dimethylaminodimethylphosphine with
triethylaluminum

2(CH )2NP(CH3)2 + A12(C2H5)6 2(CH3) NP(CH )2.Al(C2H5)3

By the vacuum method described previously 4.06 grams

(0.0386 mole) of dimethylaminodimethylphosphine was added

to 4.41 grams (0.0386 mole) of triethylaluminum in 5 ml of

toluene at -196. The mixture was allowed to warm slowly

to -780 at which temperature it was stirred for an hour.

Vacuum distillation of the light brown solution (dimethyl-

aminodimethylphosphine and the reaction product both attack









29





C(J
LO

0



(\1J


\C J
0

r-1




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3





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rC








0


o




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o
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I






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a*




ct









most stopcock greases to form a black product) yielded

5.79 grams of a colorless liquid boiling at 80.50 (0.06mm).
This corresponds to a yield of 68 per cent of theory based

on the above equation.

The infrared spectrum of the product is shown in

Figure 11. Figure 12 shows, for comparison, the infrared

spectrum of the starting material, dimethylaminodimethyl-

phosphine.

Anal. Calcd. for (CH3)2NP(CH3)2 Al(C2H5)3: C,

54.77; H, 12.41; N, 6.39; P, 14.13; Al, 12.30; mol. wt.,

219. Found: C, 54.53; H, 12.07; N, 6.29; P, 14.11; Al,

12.59; mol. wt., 213.

The proton nuclear magnetic resonance spectru- of

(CH3)2NP(CH3)2-Al(C2H )3 is found in Figure 13. This
spectrum shows three main peaks, A, B, and C, which are

attributed to the protons of the methyl groups on nitrogen,

the protons of the methyl groups on phosphorus plus the

protons of the ethyl methyl groups, and the methylene

protons, respectively. This spectrum is interesting because

it shows the splitting of the methyl protons that is brought

about by their coupling with the phosphorus atom. It is

noteworthy that the methyl groups on nitrogen are also

coupled with the phosphorus atom. Peak A results from a

singlet peak being superimposed on a double. This singlet

peak is referred to as an extraneous peak because it doesn't










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seem to belong to this molecule. This matter will be dis-

cussed later. Peak B is the doublet of the phosphorus

methyl groups superimposed on the triplet of the ethyl

methyls. Careful examination of this portion of the

spectrum shows a small concentration of a second doublet

for the phosphorus methyl protons. Peak C arises from the

methylene protons. This peak appears to be a quintet

rather than the normal quartet. This could be caused by

coupling with the phosphorus atom but this is uncertain.

Figure 14 shows the nuclear magnetic resonance

spectrum of another sample of the above reaction product

that was heated to 50 for 24 hours during the synthesis.

In peak A we note that the extraneous singlet peak is now

the major peak. Peak B contains two doublets for the

methyl groups on phosphorus and these are of about the same

concentration.

The ?31 chemical shifts are rather important in this

case because large changes are noted. The phosphorus shifts

for dimethylaminodimethylphosphine, the 1:1 unheated adduct

with triethylaluminum, and the heated adduct are: -38.5,

+40.5, and -35.5 ppm. relative to H 3PO.

A sample of the molecular addition compound was

heated to 650 on an oil bath in the dry box and held at

that temperature for 60 hours. The resulting compound was

analyzed and the n.m.r. and infrared spectra were obtained.










35




ri


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These data indicate that the product contains two ethyl

groups on the aluminum atom, two methyl groups on the

phosphorus atom, and two methyl groups on the nitrogen

atom. This material was vacuum distilled in order to

purify the product but the compound decomposed with the

evolution of a large amount of a volatile gas which was

not identified. After distillation the analysis gave an

approximate formula which was confirmed by n.m.r. as being

(CH3)2NA(2 C5)2.

The reaction of triethylaluminum with dimethylamino-

dimethylphosphine in a 2:1 molar ratio produced a material

in small yield which, after being distilled twice, had an

approximate analysis and molecular weight for the 2:1

adduct. This material could not be purified by distil-

lation, however.

The interaction of diethylaminodiphenylphosphine with
triethylaluminum

2(C2H5)2NP(C6H5)2 + Al2(C2H5)6 C2H5 + other CH compounds

+ 2(C2H5)2NP(C6H5)2Al(C2H5)2H

By the vacuum method 9.37 grams (0.0364 mole) of

diethylaminodiphenylphosphine was combined with 4.16 grams

(0.0564 mole) of triethylaluminum at liquid nitrogen

temperature. The reaction mixture was allowed to warm

slowly to room temperature and was then stirred for an

hour. During this time gas was evolved and the reaction























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Ir ~





~~- ur .-~ ..n ur~.i


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+:l l :- "ll-' l.


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methylene protons of the nitrogen ethyl group. Peak C is

attributed to two triplet peaks from the methyl protons of

the two different types of ethyl groups present. Peak D

is the normal quartet arising from the protons of the

methylene group attached to aluminum. This spectrum gives

no evidence for a single hydrogen atom being present.

If there is no single hydrogen atom present and the

compound is monomeric then the compound would have an un-

paired electron. The magnetic moment of a sample of this

compound was measured on the Gouy balance and it was deter-

mined that it is diamagnetic, therefore there are no

unpaired electrons present. This fact was confirmed by

obtaining the electron spin resonance spectrum which con-

tained no peaks indicating no unpaired electrons are

present.

The interaction of tetramethylbiDhosohine with triethyl-
aluminum

(CH3)2PP(CH3)2 + A12(C2H5)6 (CH)2PP(CE3)22Al(C2H5 3

By the vacuum method an excess of tetramethylbi-

phosphine was condensed onto 1.63 grams (0.0143 mole) of

triethylaluminum at liquid nitrogen temperature. The

reaction mixture was allowed to warm slowly to room

temperature and was then stirred for an hour. The excess

biphosphine was removed under vacuum and the liquid product

was stirred for an additional 12 hours at room temperature.










Distillation yielded 1.64 grams of a colorless liquid which

boils at 1020 (0.15mm), 66 per cent of theory according to

the above equation.

The infrared spectrum of this product is found in

Figure 18. Figure 19 is the infrared spectrum of tetra-

methylbiphosphine.

Anal. Calcd. for (CH-) P(CH 2A(C2H): C,

54.84; H, 12.08; P, 17.68; Al, 15.40; mol. wt., 350.

Found: C, 54.79; H, 12.26; P, 17.72; Al, 15.15; mol. wt.,

292 (Rast method, 392).

The proton nuclear magnetic resonance spectrum of

this compound is found in Figure 20. This spectrum is

composed of three peaks, A, 3, and C, which arise from the

methyl groups on the phosphorus atom, the ethyl methyl

groups, and the methyl groups. The triplet and quartet

up field are typical of ethyl groups on aluminum. The

tripling of the methyl protons on phosphorus arises from

the protons coupling with both phosphorus atoms. The

starting material, tetramethylbiphosphine, also shows this

tripling of the methyl protons.

An attempt to prepare the 1:1 molecular addition

compound by reacting tetramethylbiphosphine and triethyl-

aluminum in equimolar amounts was unsuccessful.







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The interaction of tetraohenylbiphosphine with triethyl-
a lu-minum*

2(C6H5)2PP(C6H 5)2 + Al2(C25) -

2(C65)2PP(C6H5)2.Al2(C25)3

By the vacuum method 2.26 grams (0.00610 mole) of

tetraphenylbiphosphine was added to 1.41 grams (0.00123

mole) of triethylaluminum in 8 ml of toluene at -780. The

heterogeneous mixture was stirred at this temperature for

an hour, and upon being allowed to warm slowly to room

temperature a clear solution was obtained. The toluene

was removed under vacuum and the remaining solid was trans-

ferred to the dry box and recrystallized from hot hexane.

The yield was 1.80 grams of a white crystalline solid

melting at 99-1010 (61 per cent of theory according to the

above equation).

The infrared spectrum of this compound, Figure 21,
-l
does not show the peak at 1120 cm. for tetracoordinate

phosphorus having a P-phenyl bond. Figure 22 is the infra-

red spectrum of the starting material, tetraphenylbiphos-

phine.


This compound was reported in the literature after
it had been synthesized in our laboratory (12). These
authors were concerned with the order of organometallic
reagents interacting with biphosphines to cleave the P-P
bond. The bonding in the tetraphenylbiphosphine-triethyl-
aluminum adduct was not considered, nor were spectral data
reported. The adduct was characterized by phosphorus and
aluminum analysis and the melting point.





SI r.-~r~....... I-. I.. ..1:

...... ...........1...~1. rr~......- I..


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o
i o3


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Anal. Calcd. for (CH )2 P(CH 5)2 Al(C2H5)5: C,

74.36; H, 7.28; P, 12.79; Al, 5.57; mol. wt., 485. Found:

C, 71.02; H, 6.87; P, 12.40; Al, 5.58; mol. wt., 464.

The proton nuclear magnetic resonance spectrum for

this adduct, Figure 23, consists of three peaks; a typical

phenyl peak A, a triplet B, and quintet C. These peaks

are assigned to the -henyl protons, the methyl protons and

the methylene protons, respectively. The quintet for the

methylene protons probably arises from coupling with the

phosphorus atom. This spectrum indicates that only one

type of phenyl group is present. The 31P n.m.r. spectrum

was obtained and it consisted of a single peak confirming

the fact that the phosphorus atoms are equivalent.

It should be noted that the molar ratio of triethyl-

aluminum to tetraphenylbiphosphine was 2:1 in this experi-

ment but the product obtained was the 1:1 adduct. This

indicates that under these conditions the 1:1 adduct is

the favored product.

The interaction of bis(diDhenylohosohino)ethylamine with
triethylaluminum

2C2H5N[P(C6H )2]2+ A12(C2H5)6

2C2H5N[P(C6H5)2 2A1l(C2H5 )

By the vacuum method 4.04 grams (0.00977 mole) of

bis(diphenylphosphino)ethylamine was added to 1.12 grams

(0.00977 mole) of triethylaluminum in 5 ml of toluene at


















LI\








LP
0 0







u
0



CM

lr\

0








Cs
o0











Cli





o


0











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o



.,-









-78. The reaction mixture was stirred at this temperature

for an hour and was then allowed to warm to room tempera-

ture and was stirred for an additional hour. The solvent

was then removed under vacuum and the resulting material

was transferred to the dry box where it was recrystallized

repeatedly from hexane to remove the last traces of toluene.

This procedure produced a 45 per cent yield (based on the

above equation) of a white crystalline solid melting at

78-82.

The .frared spectrum of this compound, Figure 24,
-1
does not show a peak at 1120 cm.- as would be expected if

the aluminum atom were bonded to only one of the phosphorus

atoms. The infrared spectrum of bis(diphenylphosphino)-

ethylamine is shown in Figure 25.

Anal. Calcd. for C2H5N[P(C6H5)2]2*Al(C2H5)3: C,
72.84; H, 7.64; N, 2.66; P, 11.74; Al, 5.11; mol. wt., 528.

Found: C, 73.07; H, 7.56; N, 2.87; P, 11.50; Al, 5.19;

mol. wt., 303.

The proton nuclear magnetic resonance spectrum of

this compound is found in Figure 26. The peak labeled A

arises from the protons of the phenyl groups. The rather

broad peak labeled B is attributed to the protons of the

methylene group attached to nitrogen. The C peak arises

from the methyl protons of the ethyl group on aluminum.

The D peak is attributed to both the protons of the methylene










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group on aluminum and to the protons of the methyl portion

of the ethyl group on nitrogen. This is the only spectrum

examined in this study that contains the ethyl triplet and

quartet shifted down field so that the methyl of the

nitrogen ethyl falls in the same general area as the

methylene group attached to aluminum. This spectrum indi-

cates that only one type of phenyl group is present and

this implies that there is only one type of phosphorus

atom in the molecule. The 3P n.m.r. spectrum shows only

one peak for phosphorus confirming the fact that the

phosphorus atoms are equivalent.

The interaction of bis(dithenylohosohino)methylamine with
triethylaluminum

2CH [P(C6H) 2]2 + Al (C2H) -

2CH N[P(C6H5)2]2.Al(C2H5)3

By the vacuum method described previously 2.26 grams

(0.00566 mole) of bis(diphenylphosphino)methylamine was

added to 1.29 grams (0.0113 mole) of triethylaluminum in

5 ml of toluene at -75. The reaction mixture was stirred

at this temperature for an hour and was then allowed to

warm to room temperature and was stirred for an additional

hour. The solvent was then removed under vacuum and the

resulting crystals were transferred to the dry box. Re-

crystallization from hexane yielded 2.3 grams, 80 per cent

of theory, of a white crystalline solid melting at 130-1320.









Figure 27 shows zhe infrared spectrum of this

compound and again we notice that the peak at 1120 cm.-

is missing. The infrared spectrum of bis(diphenyl-

phosphino)methylamine is found in Figure 28.

Anal. Calcd. for CH NEP(C,5)2]2-A(C2H5) : C,

72.49; H, 7.46; N, 2.73; P, 12.06; Al, 5.25; mol. wt., 514.

Found: C, 72.50; E, 7.43; N, 2.94; P, 11.83; Al, 5.60;

mol. wt., 422.

The proton nuclear magnetic resonance spectrum is

shown in Figure 29 and again we see that the phenyl groups

are all equivalent. Peak A is attributed to the protons

of the phenyl groups. Peak B is a triplet arising from

the protons of the nitrogen methyl group coupling with the

two phosphorus atoms. Peaks C and D are the triplet and

quartet peaks of the ethyl groups on aluminum. The

phosphorus n.m.r. spectrum shows only one peak confirming

the fact that both of the phosphorus atoms are equivalent.

It is notable that the 2:1 molecular addition

compound was not formed in this reaction.

The interaction of bis(diohenylDhosohino)amine with tri-
e hylaluminum

2HN[P(C6H5)2]2 + Al2(C2H5)6-2C2 6

+ [(C2H5)2AIlNP(C6H5)202]2

By the method used previously 4.75 grams (0.2123

mole) of bis(diphenylphosphino)amine was added to 1.41 grams












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(0.0125 mole) of triethylaluminum in 5 ml of toluene at

-78. The heterogeneous mixture was stirred at this

temperature for an hour and was then allowed to warm slowly.

At about -100 all the solid material dissolved in the pale

yellow solution. Upon allowing the solution to warm to

room temperature the evolution of gas commenced. Stirring

at room temperature for four hours produced 0.0049 moles of

ethane gas. The reaction flask was then heated with a

water bath to 500 for an hour, yielding a total of 83 per

cent of the theoretical amount of ethane based on the above

equation. After removal of the toluene the white crystal-

line solid was transferred to the dry box and analyzed

without further purification. The yield was 5.5 grams (94

per cent) of a white crystalline solid melting with

decomposition at 1890.

The infrared spectrum, Figure 50, does not show a
-l
peak at 1120 cm. indicating that the normal tetracoordi-

nate phosphorus having a P-phenyl bond is absent from the

molecule. The infrared spectrum of HN[P(C6H5)2]2 is found

in Figure 51.

Anal. Calcd. for [(C2H5)2 AlNP(C6H )22]2: C,

71.63; H, 6.44; N, 2.98; P, 13.20; Al, 5.75; mol. wt., 959.

Found: C, 71.93; H, 6.67; N, 3.04; P, 12.91; Al, 5.88;

mol. wt., 870.









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The nuclear magnetic resonance spectrum of this

compound was not determined because the compound decomposes

in deuterated chloroform.

Table 1 is a compilation of the infrared spectral

data obtained in this study. The peak in the region of
-l
1120 cm. has been assigned to a tetracoordinate phos-

phorus atom by Sheldon and Tyree (20). This assignment

was modified by Hart and Sisler to limit it to a tetraco-

ordinate phosphorus atom having a P-phenyl bond (19).

Paciorek and Kratzer noted the formation of this peak but

they attributed it to the formation of pentacovalent rather

than tetracoordinate phosphorus (21).

Table 2 is a compilation of the infrared assign-

ments from Bellamy's book (22) on infrared spectra with

the exception of the PN assignments. It is difficult to

make assignments for the PN absorptions because the range

over which they occur is rather large. Mayhood and Harvey
-i
assign peaks in the region 730-704 cm. to the PN stretch.

The (CH3)2N-P group has several peaks assigned; 1316-1280,
-1
1190, and a peak at 1064 cm.1 which is characteristic for

this group (23). McIvor and Hubley have examined the

(C2H )2-T? group and noted the following peaks: 1210, 1175,

and the range 740-715 cm."- (24).

Table 3 is a compilation of the nuclear magnetic

resonance data obtained in this study. This table provides













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examples of the relationship between the chemical shift

value and the electronegativity of the atom to which the

hydrogen atom is bonded. The basic observation is the fact

that as the electronegativity, or the electron density is

increased on the adjacent atom to which the hydrogen is

bonded, the peak is shifted down field. Conversely, as

the electron density on the adjacent atom is decreased, the

peak is shifted up field. For instance, the peak for the

methylene protons of an ethyl g:u- "-cned to nitrogen

atoms are down field while the peak for the protons of a

methylene group attached to a carbon atom are up field.

This effect is noticeable ov several bonds; for instance

note the locations or shift values for the protons of:

(a) a methylene group attached to nitrogen; (b) a methylene

or a methyl group attached to carbon, and (c) a methylene

group attached to aluminum. We find that: the peaks for

the protons of the methylene groups attached to nitrogen,

the most electronegative atom considered, lie furthest

down field; the peaks for the protons of methylene or

methyl groups attached to carbon lie up field from the

nitrogen methylene groups; and the peaks for the protons

of the methylene groups attached to aluminum, the most

electropositive atom considered, lie furthest up field from

the nitrogen methylene groups. The peaks for hydrogen

atoms in aromatic ring systems usually lie down field beyond

ane peaks for hydrogen atoms attached to nitrogen.








67

The most noticeable shift is that of the methylene

protons in the ethyl groups bonded to aluminum atoms. The

normal ethyl pattern is a triplet for the methyl protons

and a quartet for the methylene protons with the quartet

peak lying down field from the triplet peak. We note,

however, that the low electronegativity of the aluminum

atom causes the pattern to be inverted, that is, the

quartet peak is shifted up field from the triplet peak.












DISCUSSION AND CONCLUSIONS


Studies with aluminum alkyls have shown that hydro-

carbon elimination occurs when electron donors, such as

amines or hydrazines, containing a hydrogen atom bonded to

the nitrogen are reacted with aluminum alkyls. The re-

action of triethylaluminum with isopropylaminodiphenyl-

phosphine yields a trimeric material, with the formula

[(CH3)2CHNiAl(C2H 5)2}P(C6H5)2]3, after undergoing ethane

elimination. The trimeric nature of this compound appears

to be similar to the known trimeric compound [H2AlP(C2H5)2]3

(9) which exists in the form of a six-membered ring. The

infrared spectrum of this aminophosphine derivative shows
-i
a peak at 1120 cm.- which is assigned to a tetracoordinate

phosphorus atom containing a P-phenyl bond (19). This

infrared evidence indicates that the aluminum is bonded to

the phosphorus as well as to the nitrogen atom and, there-

fore, this compound probably exists as a nine-membered ring

as shown below:










C r7

C 2- --C
I 2"5 6 CCH



62 5







The reaction of tertiarybutylaminodiphenylphosphine

with triethylaluminum yields the molecular addition com-

pound at room temperature. This material is not stable

above room temperature. It is interesting to note that
C CAl H

















this adduct does not show the Deak at 1120 cm. in the

infrared spectrum. This indicates that the normal tetra-
C 2 5 H 2 2 5



















coordinate phosphorus is missing from this compound. It

should be noted, however, that when tertiarybutylaminodi-

phenylphosphine is reacted with chloramine the resulting
H 6 H 5












product is aminon of tertiarybutylaminodiphenylphosphonine









chloride [t-C HP2CI (19), indicating that
wthe most basic site in the moleculecular is the phosphorus
pound at room temperature. This material is not stable

above room temperature. It is interesting to note that

this adduct does not show the Deak at 1120 cm.-1 in the







infraredatom. If we accept this evidence that the most basic site

coordin the inate phosphorus is missing fromolecule is the phosphorus atom then
should be noted, however, that when tertiarybutylaminodi-






we would expect a strong ewis acid such asmine the resultinghyl-

prodaluminum to react at the phosphorus atom.henylphosphonium
chloride [t-C4H 9HP(CgH5)2(N:2)]C1 (19), indicating that

the most basic site in the molecule is the phosphorus

atom. If we accept this evidence that the most basic site

in the aminophosphine molecule is the phosphorus atom then

we would expect a strong Lewis acid such as triethyl-

aluminum to react at the phosphorus atom.










If we examine the infrared spectrum of the free

base and compare the N3 and P-phenyl absorptions with the

same absorptions in the triethylaluminum adduct we note
-1
that the TH peak at 3420 cm. in the free base is shifted
-I
to 3460 cm. in the adduct and the ?-phenyl peak at

1430 cm.- in the free base is shifted to 1440 cm. in

the adduct. Both groups seem to be affected by the presence

of the triethylaluminum moiety. Bellamy (22) notes that as

the polar character of a bond is decreased the vibrational

frequency frequently rises. Both of the peaks mentioned

have been shifted to shorter wavelength, or higher

frequency, as compared with the peak in the pure amino-

phosphine. These facts, coupled with the fact that the
-l
peak for tetracoordinate phosphorus, at 1120 cm. in the

infrared spectrum, is missing, leads one to consider the

possibility of the aluminum forming a bond with both the

nitrogen and the phosphorus atoms. If such is the case,

the aluminum, nitrogen and phosphorus atoms form a three-

membered ring and the normal peak for the tetracoordinate

phosphorus atom containing a P-phenyl bond may be shifted.

The question might arise as to whether a tetraco-

ordinate phosphorus atom having a ?-phenyl bond would be
-i
expected to show the peak at 1120 cm. in the infrared

spectrum if an aluminum atom were bonded to it. Since the

aluminum-phosphorus bond would reduce the electron density










on the phosphorus atom one might argue that the normal peak

for tetracoordinate phosphorus would be shifted by the

presence of the aluminum atom. An answer to this argument

is the fact that the compound [(CH-)2CH'Al(C2H5)2?P(C6H5)2]5

does show the normal peak for tetracoordinate phosphorus

having a P-phenyl bond at 1120 cm. -.

When tertiarybutylaminodiphenylphosphine-triethyl-

aluminum is warmed above room temperature a slow evolution

of ethane begins. After the gas evolution has ceased the re-

sulting compound has the formula (CH 3)3CN[Al(C2H5)2]P(C65)2.

This monomeric compound is in contrast to the trimeric ring

compound formed from the reaction of isopropylaminodiphenvl-

phosphine with triethylaluminum. Another contrasting
-l
feature is the absence of the peak at 1120 cm.- in the

infrared spectrum. If we examine the P-phenyl absorption
-l
in this compound we see that it falls at 1440 cm. as it

does in the 1:1 adduct. This is not a large shift but it

leads one to consider the possibility of the aluminum atom,

which is already bonded to the nitrogen atom, also inter-

acting with the phosphorus atom. If this situation does

exist the strained bond angles might account for the absence

of the normal tetracoordinate phosphorus peak.

It was thought that the phosphorus nuclear magnetic

resonance spectrum might help to clarify this point by

showing the change in the phosphorus chemical shift between










the free aminophosphine, the triethylaluminum adduct, and

the resulting compound having aluminum bonded to nitrogen.

However, upon examining all the evidence it was determined

that the chemical shift values do not yield a clear verdict

in this matter. After more examples are reported it might

be possible to make predictions but at present a definite

trend is not observed.

Polynuclear electron donor species such as amino-

phosphines, bis(phosphino)amines, and biphosphines that do

not contain a hydrogen atom bonded to the basic atoms would

be expected to react with triethylaluminum to form a

product containing an aluminum atom bonded to each basic

site, provided the proper amount of triethylaluminum is

used and steric interactions do not prohibit such bonding.

In this study the only polynuclear base that reacted with

triethylaluminum in this manner is tetramethylbiphosphine.

(Dimethylaminodimethylphosphine yielded a small amount of

material that had the approximate composition for a 2:1

adduct but it could not be purified by distillation.) Burg

(25) has shown that tetramethylbiphosphine reacts with di-

borane to form both the mono- and the di-adducts,

(CH 0PP (CH 3)2H and (CH )2PP(CH )2 2BH3. This confirms

the fact that both the phosphorus atoms in tetramethylbi-

phosphine have the ability to donate a pair of electrons

to an electron acceptor. Garrett and Urry (26) have










synthesized a molecular addition product with the formula

322?(H3))2 2CC)3 This provides another example of

both phosphorus atoms acting as basic centers. In the

light of these experiments it is interesting to note that

when tetramethylbiphosphine is reacted with triethylaluminum

the 1:1 reaction product could not be isolated under the

conditions of our experiments.

The interaction of triethylaluminum with tetraphenyl-

biphosphine was studied in our laboratory just prior to a

paper being published by Issleib and Krech (12) which des-

cribes the synthesis of the 1:1 adduct. Since these

authors did not consider the bonding in this molecule we

are including all the information obtained in our study.

The most important difference we note when comparing the

tetramethylbiphosphine adduct with the tetraphenylbiphos-

phine adduct is the fact that tetramethylbiphosphine forms

only a 2:1 addition compound whereas tetraphenylbiphosphine

forms only the 1:1 addition compound. At first we are

tempted to say that steric interactions prevent two tri-

ethylaluminum groups from bonding to the biphosphine

because of the size of the phenyl groups. An examination

of a model of the tetraphenylbiphosphine-triethylaluminum

1:1 adduct indicates, however, that there is room for

another triethylaluminum group. Another interesting fact

is that the infrared spectrum of the 1:1 adduct does not










contain the normal tetracoordinate phosphorus peak that we

would expect to find if the aluminum were bonded to only

one phosphorus atom.

An examination of the proton nuclear magnetic

resonance spectrum of the tetraphenylbiphosphine-triethyl-

aluminum 1:1 adduct indicates that all the phenyl groups

are equivalent. If the aluminum were bonded to only one

of the phosphorus atoms, the phenyl groups attached to the

phosphorus would be expected to show two peaks in the

spectrum because the environment of the two phenyl groups

attached to the quadruply bonded phosphorus should differ

from that of the two attached to the triply bonded phos-

phorus. It has been pointed out previously (1), however,

that there is an alternative to this explanation of the

n.m.r. results. This alternative involves the very rapid

transfer of alkylaluminum groups from one phosphorus atom

to the other phosphorus atom in the biphosphine addition

compound. If the rate at which such exchange occurs were

greater than the frequency separation of the resonance

peaks corresponding to the two environments of the phenyl

groups, then the two peaks would merge into a single peak

of intermediate chemical shift.

In the case of the tetramethylhydrazine-triethyl-

aluminum 1:1 adduct it was impossible to prove which

situation really exists but in the case of the tetraphenyl-

biphosphine-triethylaluminum 1:1 adduct there are other










tools available that have allowed us to resolve this

question. The first of these tools is the 31P nuclear

magnetic resonance spectrum. (Our laboratory is not

equipped to obtain the nuclear magnetic resonance

spectrum.) The phosphorus n.m.r. spectrum of tetraphe--l-

biphosphine-triethylaluminum contains only one peak

indicating that there is only one type of phosphorus

present. If the aluminum were bonding to first one

phosphorus atom and then the other we would expect to see

two peaks because the quadruply bonded phosphorus would

have a different environment than the triply bonded

phosphorus. The phosphorus n.m.r. carries more weight

than the proton n.m.r. because in the case of the bi-

phosphine the chemical shift of the phosphorus atoms is

larger than the chemical shift of hydrogen atoms and,

therefore, one might expect to see two peaks rather than

one of intermediate chemical shift if the aluminum were

rapidly bonding to first one phosphorus atom and then to

the other. The existence of only one peak in the phosphorus

n.m.r. indicates that both phosphorus atoms have the same

environment and therefore the phosphorus atoms are sym-

metrically located with respect to the aluminum atom, and

therefore the aluminum atom is pentacoordinate.

The other tool we can utilize in determining the

nature of the bonding in the tetraphenylbiphosphine-tri-

ethylaluminum adduct is the infrared spectrum. It has been











mentioned previously that a normal tetracoordinate

phosphorus atom containing a P-phenyl bond exhibits a peak
-1
in the infrared spectrum at about 1120 cm. It has also

been suggested that if a tricoordinate phosphorus atom

became tetracoordinate through the formation of a small

ring the resulting tetracoordinate phosphorus atom would

not be expected to absorb infrared energy at the same

frequency as a normal tetracoordinate phosphorus atom. If

the triethylaluminum group were exchanging between the two

phosphorus atoms in tetraphenylbiphosphine the infrared

spectrum would show the normal peak associated with tetra-

coordinate phosphorus because infrared, unlike n.m.r., is
-i
a rapid experiment. Since there is no peak at 1120 cm.-

in the infrared spectrum this compound may be assumed not

to contain the normal tetracoordinate phosphorus. In this

case the combination of infrared and n.m.r. evidence seems

to prove the pentacoordinate character of the aluminum

atom because:

First, the proton n.m.r. spectrum shows all the

phenyl groups to be equivalent.

Second, the 31P n.m.r. spectrum shows both the

phosphorus atoms to be equivalent.

Third, the infrared spectrum does not show a peak
-l
at 1120 cm.-I which is associated with the normal tetra-

coordinate phosphorus containing a P-phenyl bond.










Therefore, considering these points we may conclude

that the phosphorus atoms are symmetrically located with

respect to the aluminum atom. This must be considered as

proof of the pentacoordinate character of the aluminum atom.

-Wen a nitrogen atom is substituted for a phosphorus

atom in tetramethylbiphosphine the resulting molecule is

dimethylaminodimethylphosphine (27). The reactions of di-

methylaminodimethylphosphine would be expected to be

similar to the reactions of tetramethylbiphosphine due to

structural similarities. Holmes and Wagner have shown

that dimethylaminodimethylphosphine reacts with trimethyl-

and triethylboron to form 1:1 adducts (28). It has also

been shown that dimethylaminodimethylphosphine reacts with

diborane to form both the 1:1 and the 1:2 adducts,

(CH3)2N(CH3)2.-3 and (CH )2::P(CH3)2-2BH3 (29). In the

work of Holmes and Wagner the reaction of trimethylboron

with dimethylaminodimethylphosphine also produced the pro-

ducts of cleaving the PN bond, that is, (CH )NB(CH)2 +

(CH ) P-B(C:,). We have shown that triethylaluminum

reacts with dimethylaminodimethylphosphine to form the 1:1

adduct and have indications that the 2:1 adduct might be

formed.

The pro-on n.m.r. for the 1:1 adduct with triethyl-

aluminum, Figure 13, shows one extraneous peak in the region

of the double peak assigned to the methyl groups attached











to nitrogen. This spectrum should be compared with Figure

14 which is the spectrum of a product synthesized by the

same method except that the material was heated to approxi-

mately 500 for 24 hours prior to distillation. The boiling

point of this material is the same as the material shown to

be the 1:1 adduct. The infrared spectrum of this heated

material is identical with the spectrum of the unheated

material except that the absorption of two of the peaks is
-i
increased. The weak peak at 745 cm. is increased to a
-l
medium peak and the strong peak at 1230 cm. is increased

to a very strong peak. The n.m.r. spectrum shows a con-

siderable change, however. The intensity of the doublet

peak, which arises from the protons of the methyl group

on nitrogen, has decreased considerably and the singlet

peak, which had been the extraneous peak, has increased

tremendously. The P n.m.r. spectrum shows the phosphorus

peak of the heated material to have about the same chemical

shift as the free base. This information leads one to

postulate that the extraneous peak is caused by a tautomer

in which the aluminum is bonded only to the nitrogen atom

rather than to the phosphorus atom or to both the nitrogen

and the phosphorus atoms. If the aluminum atom is bonded

to the nitrogen atom the electron density on the nitrogen

would be reduced and we might predict that this would

inhibit the coupling of the nitrogen methyl protons with










the phosphorus. This would account for the singlet peak

referred to above as the extraneous peak. Roberts has

pointed out that shift values can be utilized as a measure

of electron density or electronegativity (50). The fact

that the extraneous peak is shifted up field compared with

the original doublet can be explained by the fact that the

electron density on the nitrogen would be reduced by having

an aluminum atom bonded to it.

On the basis of the above discussion the 1:1 adduct

is really a mixture which contains approximately 80 per

cent of the aluminum atoms bonded to phosphorus and 20 per

cent bonded to nitrogen. In order to determine the extent

of this heat effect a sealed tube containing a sample of

the unheated 1:1 adduct was heated to 700 for 50 hours.

The n.m.r. spectrum of the sample was obtained at room

temperature periodically during this 50-hour period. After

50 hours of heating the singlet peak had increased in size

compared to the doublet peak to indicate a 95 per cent

concentration of the material postulated to contain an

aluminum-nitrogen bond.

It is possible that the kinetics of the initial re-

action favor formation of the phosphorus-aluminum bond but

that the nitrogen aluminum bond is thermodynamically more

stable. In any case, it is apparent that two products are

being formed and that the product responsible for the

anomolous peak is being generated as the mixture is heated.










An attempt to produce a larger sample of the material

presumed to contain an aluminum-nitrogen bond resulted in

the pyrolysis of the 1:1 adduct. This was evidenced by the

formation of a compound which n.m.r. and elemental analysis

indicate is probably (CH3 )2P[A(C2Hr5)2]N(CH )2. This

formula leaves an unpaired electron in the molecule so it

is thought that the compound is probably a dimer. This

material was pyrolyzed further when distillation was

attempted. The principal distillation product contains

only a small amount of phosphorus. Elemental analysis and

proton n.m.r. spectroscopy indicate that this material is

impure dimethylaminodiethylalane, (CH )2NAl(C2H5)2. This

product would be in accord with the reaction of dimethyl-

aminodimethylphosphine with trimethylboron (28).

(CH3)2 P(CH )2 + 2B(C 3) (CH )2I(CH)2

+ (CH 3)3PB(CH3)3

The interaction of diethylaminodiphenylphosphine

with triethylaluminum is very interesting in as much as a

simple molecular addition compound is not obtained. The

reaction proceeds with the elimination of a mixture of

hydrocarbon compounds, ethylene being the only one posi-

tively identified. The proton n.m.r. spectrum of the

distilled product gives a great deal of information con-

cerning what has taken place in the reaction. This










spectrum indicates that there are two ethyl groups on the

nitrogen atom, two ethyl groups on the aluminum atom, and

two phenyl groups on the phosphorus atom. This indicates

that aluminum has lost an ethyl group perhaps in a growth

type reaction such as that shown by the following equations

(31):
Al ( C'T HA1( H
Al(C2) EAl(c25)2 C2

Al(C2H5)3 + CH- Al(C2H )(CH9)

Al(C2H ))(Ca 9) HAl(c2 5)2 + C4-8

Heating the original reaction mixture for distillation

might allow ethylene to be evolved in the known heat effect.

The ethylene could then react with the aluminum-carbon bond

in a growth reaction to form a variety of long chain sub-

stituents on the aluminum atom. This product could then

break down to yield olefins and the compound with two

ethyl groups on the aluminum atom.

The fact that the aluminum atom contains only two

ethyl groups, coupled with the molecular weight determi-

nations which show the compound to be monomeric indicate

that the product might be an odd electron molecule. The

magnetic moment of a sample of this compound was measured

on the Gouy balance and it was found that it is diamagnetic.

The electron spin resonance spectrum confirmed this fact.

Therefore, there are no unpaired electrons. This leads us








82

to postulate the presence of an unseen hydrogen atom. A

careful check of the n.m.r. and the infrared spectrum does

not reveal a single hydrogen .tom such as an AlE, an NH,

or a PH group. A single A11 peak would not readily be seen

in the n.m.r. spectrum because the spin of the aluminum

nucleus is 5/2 and thus the Al-H peak would be a multiple

resulting from coupling with the aluminum nucleus and it

would be broadened by the quadrupole moments of the

aluminum and the nitrogen. The single 'NH peak is often

too broad to be seen for reasons ,-milar to those given for

the A1H peak. A PH peak would probably be observed in the

n.m.r. spectrum because it is split by about 200-300 cycles

per second giving two peaks, and it is improbable that both

peaks would be hidden. This information explains how a

hydrogen atom could be bonded to aluminum or to nitrogen

and not be observed in the n.m.r. spectrum. This leads us

to postulate the presence of a single hydrogen atom in the

molecule, probably bonded to the nitrogen or the aluminum

atom giving the following formula for the compound:

(C2 5)2NP(C6H )2A(C25 )2H. If the hydrogen atom is

attached to the nitrogen atom the molecule would be a

Witterr ion because the nitrogen and the phosphorus would

ea-- be charged. All of this is of course speculation and

indicates the need for additional work.


























i_








x
x- .. i,
v





..-~. ....
~- , ------ - ~ --







J
) -`-` ;. - : ~
































J


















































c.










indicates that the free pair of electrons on the nitrogen

atom may be at least partially donated into the phosphorus

d-orbitals. Under these circumstances, the phosphorus

atoms would have a greater electron density and would be

stronger basic centers than the nitrogen atoms. The proton

n.m.r. spectrum of the bis(diphenylphosphino)methylamine-

triethylaluminum adduct shows all the phenyl groups to be

equivalent indicating that the phosphorus atoms have the

same environment. The phosphorus n.m.r. spectrum supports

this point of view since it shows only one kind of phosphorus

atom. The combination of all the evidence again indicates

pentacoordinate character for the aluminum atom because:

First, chloramine reacts with bis(diphenylphosphino)-

methylamine to produce a compound, shown below, in which

both phosphorus atoms have been attacked by chloramine, but

the nitrogen atom remains tricoordinate.





SP(C H52
1NH
6 ))2




Second, the proton and phosphorus n.m.r. spectra

show both phosphorus atoms to be equivalent.

Third, the infrared spectrum does not show a peak at
-l
1120 cm.- which is associated with a normal tetracoordinate

phosphorus containing a P-phenyl bond.










Therefore, considering these points we may again

conclude that the phosphorus atoms are symmetrically located

with respect to the aluminum atom. This must be considered

as proof of the pentacoordinate character of the aluminum

atom.

The reaction of triethylaluminum with bis(diphenyl-

phosphino)ethylamine is very similar to the reaction with

bis(diphenylphosphino)methylamine. The main difference is

the isolation of the reaction product. The molecular

addition compound formed with bis(diphenylphosphino)-

ethylamine tends to hold onto the toluene solvent ten-

aciously. The difficulties in removing the last traces of

toluene are responsible for the low yield as compared to

the yield of the bis(diphenylphosphino)methylamine-tri-

ethylaluminum compound. The evidence for the pentacoordi-

nate character of the aluminum atom in this compound is

similar to that for the previous compound.

The molecular addition compound was not stable at

room temperature in the case of triethylaluminum reacting

with bis(diphenylphosphino)amine. In this case the nitrogen

atom of the free base is bonded to a hydrogen atom and upon

allowing the reaction mixture to warm to room temperature

ethane gas is evolved. Molecular weight measurements on

the resulting compound indicate that it exists as a dimeric

species. An interesting conjecture concerning the structure










of -his dimer is to again consider the aluminum atom to be

pentacoordinate, bonding to two phosphorus atoms from

another monomeric species to form the dimer.



N---Al~
(C6H )2 2H5



H5C P(CH)

A model of this compound shows that the large size of the

phosphorus atoms tends to cover or hide the nitrogen atom.

For this reason steric interactions would probably prohibit

the formation of a four-membered ring between the nitrogen

and aluminum atoms. The infrared spectrum of this compound

does not show the normal tetracoordinate phosphorus peak,

so there is a good possibility that the aluminum atom is

indeed pentacoordinate in this compound.














Chemical evidence, nuclear magnetic resonance

spectral data, and infrared spectral data confirm the fact

that the reaction of triethylaluminum with several bi-

nuclear Lewis bases, which contain two diphenylphosphorus

moieties, results iA the formation of 1:1 adducts in which

the aluminum atoms are pentacoordinate. Three compounds of

this nature are described: tetraphenylbiphosphine-tri-

ethylethylaluminum, (C6 5)2PP(C6 H )2Al(C2H )3; bis(di-

phenylphosphino)methylamine-triethylaluminum,

CH3N[P(C6H5)2]2-Al(C2H5) ; and bis(diphenylphosphino)ethyl-

amine-triethylaluminum, C2H5N[P(C6E5)212-Al(C2H ) 3

Triethylaluminum reacts with tetramethylbiphosphine

to form the 2:1 adduct, (CH3)2PP(CH)2-2Al(C2H5)3, but not

the 1:1 adduct. Triethylaluminum, however, does react

with dimethylaminodimethylphosphine to form the 1:1 adduct,

((CH )2NP(CH)2-Al(C2H5)3. An attempt to synthesize the 2:1

adduct yielded a small amount of material with the approxi-

mate composition of the desired material.

The reaction of triethylaluminum with diethylamino-

diphenylphosphine yields a mixture of hydrocarbon compounds

including ethylene and a compound containing two ethyl

groups on nitrogen, two ethyl groups on aluminum and two

87









phenyl groups on phosphorus. Since this compound is not

dimeric nor paramagnetic it is postulated that there is a

hydrogen atom present that cannot be seen in the n.m.r.

or the infrared spectrum. The formula is postulated to be

(CH2 5)2P(C6 5)2Al(C2H )2H. Since the infrared spectrum
still contains the peaks of the aminophosphine spectrum,

there is no reason to believe the T? bond to be broken in

the reaction.

The reaction of triethylaluminum with tertiarybutyl-

aminodiphenylphosphine results in the formation of the 1:1

adduct, (CH 3)3CUH(C6H5)2Al(C2E 5), which is unstable

above room temperature. Heating this compound results in

the evolution of ethane to produce a monomeric compound

having aluminum bonded to nitrogen,

(CH3)3CX[Al(C2H5)2]P(C6H5)2.

The 1:1 adduct from the reaction between triethyl-

aluminum and isopropylaminodiphenylphosphine can not be

isolated at room temperature. Ethane is given off and the

aluminum atom forms a bond with the nitrogen atom producing

the following trimeric compound,

[(CHE)2CHN 1!(Cc2H5) 2P(C6H5)2]3.
Ethane is also liberated in the reaction between

bis(diphenylphosphino)amine and triethylaluminum. The

resulting product in this reaction is a dimeric material,

[(C2 5)2Al?((C6H5 ) 212,2 which might possibly be another
example of a compound containing pentacoordinate aluminum.












PART II. A STUDY O T3EE C-LORAMINAION OF SOiE
A:.I:.OPHOSHPIN:7 DERIVATIVES


INTRODUCTION


The reactions of chloramine with ohosphorus-con-

taining compounds have been the subject of study in this

laboratory for the last several years. A recent study

concerned the reactions of chloramine with aminophosphines

and showed that the effluent gases from the chloramine

generator, that is, a mixture of chloramine and an excess

of ammonia, react with aminophosphines to produce amino-

phosphonium chlorides rather than phosphinohydrazinium

chlorides (19). All the previously reported chloramina-

tions were, however, concerned with phenyl phosphino deriva-

tives and none of them contained alkyl-phosphorus bonds.

Furthermore, with the exception of l,l-bis(diphenylphos-

phino)-2,2-dimethylhydrazine (36), none of the previously

chloraminated nitrogen-phosphorus derivatives contained

more than one phosphorus atom attached to a nitrogen atom.

The present work was undertaken to determine if, as

in the case of the previously studied aminophenylphosphines,

chloramination of aminoalkylphosphines and of bis(diphenyl-

phosphino)amines occurs on the phosphorus atom(s) rather

than the nitrogen atom.







90

Historical Background

The preparation of chloramine in acueous solution

was developed by Rashig in 1907 (37) using the reaction of

ammonia and hypochlorite ion:

OC1 + 3 :i..2C1 + O

It was not until 1951 that the gas phase reaction was per-

fected allowing the convenient .preparation of anhydrous

solutions of chlorami e (88,39). This process utilizes the

reaction between chlorine _nd__n _excess of ammonia gas to

produce chloramine in accord with the following equation:

2 (g) + C12() H2Cl(S) + NH4Cl(S)

Drago (40) has reviewed the chemistry of chloramine

providing a brief discussion of the preparations and the

wide variety of reactions of chloramine. A more recent

discussion (41) provides a list of references concerning

the reactions of chloramine with trisubstituted phosphines,

and aminophosphines to produce phosphonium salts.

A recent study in our laboratory has shown that a

variety of di-, tri-, and tetraaminophosphonium chlorides

results from the chloramination of different species of

aminophosphines (19).










6--(C 5 5 )2 + :':2C1




(R2')2?(C6H5) + NiH2C1 -




(R2N) P + NHi2C1


r
-i"
S C.H

C,H-


R2N

R2

R2N


The reaction of 1,l-bis(diphenylphosphino)-2,2-di-
methylhydrazine with chloramine provides the only example
of the chloramination compound containing the P-N-P linkage
presently in the literature (36). The following reaction
sequence was postulated for this reaction:
/ 2
(C6H )2\ C (C \ CH
X-- + NH Cl N-N Cl
(C/6K5)2P C\ C
(C 6H5)2P CH (C H5 2P CH


NH2

(CG6H5)2\
N--N C + N -
( 5 CH


//NH
(C6H)2 P\ ,CH3
N-N
(C6H5)2P CH/


(C6 5 ) P


CH)
N--N
CH-
9?


(C H) /P CH
+ NKH2CI -. N-N
CH N CH
(CH ) \CH
L 65) 2\1 2 3




Full Text

PAGE 1

A STUDY OF THE REACTIONS OF SOME NITROGEN AND PHOSPHORUS BASES: (I) WITH TRIETHYL ALUMINUM; (II) WITH CHLORAMINE By DONALD FAULL CLEMENS A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA April, 1965

PAGE 3

ACKNOWLEDGMENTS The author wishes to recognize the friendly assistance and moral support of his committee during the course of this work. The encouragement and enthusiasm provided by Professor Harry H. Sisler, under whose direction this work was carried out, has been most beneficial. Although busy with administrative duties he has always had time to listen to the author's problems with an attentive ear and has always been helpful in obtaining the solutions to these problems. Professor Wallace S. Brey has been of special assistance in obtaining and interpreting nuclear magnetic resonance spectra for this study. The author is indebted to his colleagues, Mr. Stephen E. Frazier and Mr. PLObert L. McXenney, for the many challenging discussions and ideas shared during the course of this work. Acknowledgment is made to the donors of The Petroleum Research Fund, administered by the American Chemical Society, for support of this research. Finally, the author wishes to express his gratitude to his wife Kay, and his five children for their many personasacrifices. Without their encouragement this work would not have been possible. ii

PAGE 4

TA3LE OF CONTENTS Page ACKNOWLEDGMENTS ii LIST OF TABLES iv LIST OF FIGURES v PART I. A STUDY OF THE SYNTHESIS OF SOME ALUMINUM DERIVATIVES OF PHOSPHORUS AND NITROGEN INTRODUCTION 1 Historical Background 2 EXPERIMENTAL 6 DISCUSSION AND CONCLUSIONS 68 SUMMARY 87 PART II. A STUDY OF THE CHLORAMINATION OF SOME AMINOPHOSPHINE DERIVATIVES INTRODUCTION 89 Historical Background 90 EXPERIMENTAL 93 DISCUSSION AND CONCLUSIONS 132 SUMMARY 138 BIBLIOGRAPHY 141 BIOGRAPHICAL SKETCH 144 in

PAGE 5

Table LIST 0? TABLES -1 Infrared Absorption in Cm." (Part I) 2. Infrared Absorption Assignments, 5. Nuclear Magnetic Resonance Data (Part I) b r. Infrared Absorption in Cm." (Part II) . 5. Nuclear Magnetic Resonance Lata (Part II) Page 9 14 64 128 1J0 IV

PAGE 6

• -re Page 1. Vacuum line 7 2. Infrared soectrum of [(ck 5 ) 2 ch^{;ai(c 2 h 5 ) 2 ^?(c 6 h 5 ) 2 ] 3 17 3. Infrared spectrum of (CH Z ) CKNH?(C H-) .... IS 3 d b p d 4. Infrared spectrum of A1 (C H C )^ 19 5. ( H) ITuclear magnetic resonance spectrum of [( :>::: [a:(C 9 :-:-) 9 } ?;G-H-)j/in benzene. . 21 6. Infrared soectrum of CGK,),CIIH?tc,,H l -)5-Al(C E-), 23 7 3 j o p 2 v 2 /3 Infrared soectr ' Z':.~ ) -,CXH?(C -H .) -. 24 8. ( H) Nuclear cic resonance soectrum of (CH,),C:iH?(C^H -Al(C . . / 3 3 o p 2 2 7 p 9. In strum of (ce 3 ) 3 c:t[aI(c ] 27 2_ 10. ( X H) :• • :onance spectrum of W--?; 7 -••---— . -? 11. la spectrum of ( : •Al(C ? H £ -) 7 31 L . Infrared spectrum of ( \ f?(fH 7 ) 32 j -T»nm -it" ' n " " ' " ^Q 16. Infrared .^ v ^-/p V

PAGE 7

Figure Page 17. ( H) Nuclear magrieii-c resonance spectrum of (C 2 H 5 ) 2 NP(C 6 H 5 ) 2 A1(C 2 H 5 ) 2 H 40 18. Infrared spectrum of (CE 3 ) 2 ?P(CE 3 ) 2 -2A1(C 2 E 3 ) 3 43 19. Infrared spectrum of (CH,) 2 PP(CH,) 2 44 20. ( H) Nuclear magnetic resonance spectrum of (CH 5 ) 2 ?P(CH 3 ) 2 -2A1(C 2 K 5 ) 3 45 21. Infrared soectrum of (C 6 H 5 ) 2 ?P(C 6 E 5 ) 2 -A1(C 2 H 5 ) 5 47 22. Infrared spectrum of (C 6 E 3 ) 2 PP(C 5 E 3 ) 2 48 23. ( H) Nuclear magnetic resonance spectrum of (C 6 H 5 ) 2 ?P(C 6 H 5 ) 2 -A1(C 2 H 5 ) 5 50 24. Infrared soectrum of C 2 H 5 N[P(C 6 H 5 ) 2 ] 2 -A1(C 2 H 5 ) 3 52 25. Infrared spectrum of CpE,-N[P(C,-Ec-)p]p 53 28. ( H) Nuclear magnetic resonance spectrum of C 2 H 5 [P(C 6 H 5 ) 2 ] 2 -A1(C 2 E 5 ) 5 54 27. Infrared spectrum of CH 5 N[P(C 6 Hc)p] 2 'Al(C 2 H,-) 5 37 28. Infrared spectrum of CH 3 N[P(C 6 H,-) 2 ] 2 58 29. ( H) Nuclear magnetic resonance soectrum of CH 3 N[P(C 6 H 5 ) 2 3 2 'A1(C 2 H 5 ) 3 59 30. Infrared spectrum of [(C 2 E 3 ) 2 A1N{?(C 6 E 3 ) 2 } 2 ] 2 . 61 31. Infrared spectrum of HN[P(CgH,-) 2 ] 2 62 32. Infrared spectrum of C 2 H 5 NHP(C^Hq) 2 97 33. ( H) Nuclear magnetic resonance spectrum of C 2 H 3 NHP(C^H 9 ) 2 98 34. Infrared spectrum of C ? E 3 N[P(C 6 E 3 ) 2 ] 2 100 35. ( H) Nuclear magnetic resonance spectrum of C 2 H 5 N[P(C 6 E 5 ) 2 ] 2 101 VI

PAGE 8

Figure 36. 37. 38. 39. 40. 41. 43. 44. 45. 46. Infrared spectrum of CH,N[P(C,-Ht)pJp . . . . ( H) Nuclear magnetic resonance soectrum of ch 5 :t[?(c 6 h-) 2 ] 2 Infrared spectrum of EN[P(C^E;-)p]p . . . . . The chloramine generator , Infrared spectrum of [ (NS 2 ) f(CE 3 ) 2 N}p(CE 3 ) 2 ]Cl ( E) Nuclear magnetic resonance spectrum of [(NH 2 )-[(CH 3 ) 2 N}P(CH 3 ) 2 ]C1 ( H) Nuclear magnetic resonance soectrum of (CH 3 ) 2 FP(CH 3 ) 2 Infrared spectrum of [(NE 2 ) (C 2 E 5 NE)P( C^Hq) 9 ]C1 ( H) Nuclear magnetic resonance spectrum of [(NE 2 )(C 2 E 5 NE)P(C^E 9 ) 2 ]C1 Infrared spectrum of Page 103 104 106 108 110 111 112 113 116 118 NE P(C 6 H 5 ) 2 CI C 2 E 5< >C & Ep) 2 NE 2 ( E) Nuclear magnetic resonance spectrum of 1 i y NE ,P(C 5 E 5 ) 2 C 2 E 5 N N I o yd CI 119 NE. 47. Infrared spectrum of ii CH 3\ P(C 6 H 5 ) 2 P(C 6 E-) 2 I NE ? 121 CI VI i

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Figure Page -!„ 4-3. ( H) Nuclear magnetic resonance spectrum of i y NH li ,P(C 6 H 5 ) 2 CH,N 3 \ ?(C 6 H 5 ) 2 m. ci 123 4-9. Infrared spectrum of [(C 6 H 5 ) 2 ?(::h 2 )::p ^ TH 2 )(C 6 H 5 ) 2 ]C1 * hcc1 3 12 5 50. Infrared spectrum of [(C 6 H 5 ) 2 P(KH 2 )1TP(NH 2 )(C 6 H 5 ) 2 ]C1 126 51. ( E) Nuclear magnetic resonance spectrum of [(C 6 H 5 ) 2 ?(NH 2 )NP(im 2 )(C 6 K 5 ) 2 ]Cl 127 Vlll

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PART I. A STUDY 0? THE SYNTHESIS 0? SOME ALUMINUM DERIVATIVES OF PHOSPHORUS AND NITROGEN INTRODUCTION Recent studies in this laboratory of the reactions of triethylaluminum and ethyl aluminum chlorides with hydrazines have shown that if one or more of the groups bonded to a nitrogen atom is a hydrogen atom, hydrocarbon elimination takes place. If there is no hydrogen available on the nitrogen atom the reaction proceeds to form a molecular addition product. Tetramethylhydrazine reacts with alkyl aluminum compounds to form adducts which have been postulated to contain pentacoordinate aluminum (1,2). The existence of pentacoordinate aluminum has been proved by the reactions of aluminum hydrides with two moles of amine to form 1:2 complexes (3,4,5). ^ was thought that the reactions of triethylaluminum with aminophosphines and biphosphines might be very similar to its reactions with hydrazines. An aminophosphine would provide several possibilities for reaction: the aluminum atom could become attached to the nitrogen atom, to the phosphorus atom, or to both atoms. If both the nitrogen and phosphorus atoms function as electron donor centers it

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night be possible to attach two molecules of an alkylaluminum compound to one molecule of the aminophosphine. This study was conducted to determine how triethylaluminum would interact with molecules containing more than one basic center, to determine the nature of the reaction products and to examine the possibility of the existence of pentacoordinate aluminum in these compounds. Historical Background The literature contains many references to aluminumhydrogen or aluminumcarbon compounds reacting with nitrogen-containing electron donor species. With the exception of two aryl aluminum compounds reported in 1930 (6), all such references appeared after the exploratory work of Davidson and Brown in 19^-2 (7). Davidson and Brown synthesized alkylaluminum derivatives of trimethylamine, trimethylphosphine, dimethyl ether, and dimethyl sulfide. The large number of reports concerning aluminumnitrogen chemistry is in sharp contrast to the relatively small number of papers dealing with the reactions of aluminum hydride or aluminum alkyls with phosphoruscontaining bases. The aluminum-phosphorus compounds reported as products of such reactions can be placed in four categories. In each case an example is given.

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1. Molecular addition compounds of trialkylphosphines with aluminum hydride or aluminum alkyls (7,3). A1 2 (CH $ ) 6 + 2(CH 5 ) 3 ? 2(CH 3 ) 3 ?-A1(CH 3 ) 3 2. Alkylphosphinoaluminum hydrides (9,10). 3H 2 A1C1 + 3Li?(C 2 K 5 ) 2 [H 2 A1P(C 2 H 5 ) 2 ] 5 + $LiGl 3. Alkyland arylphosphinoaluminumalkyls or alkylaluminum phosphides (11). (C 2 H 5 ) 2 A1C1 + CH 3 ?(C 2 K 5 ) 2 (C 2 K 5 ) 2 A1?(C 2 H 5 ) 2 + CH $ C1 4. Molecular addition compounds of biphosphines with aluminum alkyls (12). 2(C 6 H 5 ) 2 PP(C 6 H 5 ) 2 + A1 2 (C 2 H 5 ) 6 2(C 6 H 5 ) 2 ??(C & H 5 ) 2 .A1(C 2 K 5 ) 3 . The interaction of polynuclear electron-donor molecules with aluminum alkyls was until recently unexplored. Within the last four years, however, a number of papers concerning interactions of aluminum alkyls with polynuclear bases have appeared. Paterson and Onyszchuk synthesized an extremely shock sensitive compound, with the formula (CH 3 ) P A1NKNHA1(CK 3 ) 2 , by allowing trimethylaluminum to react with hydrazine (13). A1 P (CH 3 ) 6 + l\ T 2 K a 2CH^ + (GH 3 ) 2 A1^HXHA1(CH 3 ) 2

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The interactions of methylhydrazines with aluminum alky Is nave been studied by several research groups. Fetter and Bartocha (2) have synthesized a number of compounds by the reactions of trimethyl aluminum and trimethylaluminumtrimethyl amine with methylhydrazine, 1 ,2-dimethylhydrazine, 1 ,1-dimethylhydrazine, trimethylhydrazine, and tetramethylhydrazine. (CH,) 3 A1-N(CH 5 ) 5 + HN(CH 5 )N(CH 5 ) 2 (CH 5 ) 5 A1-NH(CH 5 )N(CH 5 ) 2 + N(CH $ ) 3 A1 2 (CH 5 ) 6 + 2H 2 NN(CH,) 2 [(CHOgAlHHNCCH^glg + 2CH^ These investigations were extended in our laboratories by a study of the interaction of triethylaluminum with 1 ,1dimethylhydrazine (14) an 3by the interaction of 1,1-dimethylhydrazine and tetramethylhydrazine with ethyl and ethylchloroaluminum compounds (1). The product of the reaction of ethylaluminum dichloride with trimethylhydrazine was also isolated and characterized A1 2 (C 2 H 5 ) 4 C1 2 + 2H 2 M(CH 5 ) 2 [C^AlClNHl^CHj)^ + 2C H ft A1 2 (C 2 H 5 ) 6 + 2(CH 5 ) 2 NM(CH $ ) 2 2(CH 3 ) 2 NN(CH 5 ) 2 . Al (C^) ? . It has been shown that trimethyl and triethylaluminum react with tetramethylethylenediamine, tetraethylethylenediamine, and tetramethylmethylenediamine to form complexes

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which, contain two moles of aluminum per mole of diamine (15,16). ai 2 (c 2 h 5 ) & + (ch $ ) 2 n(ch 2 ) 2 :t(ch 3 ) 2 (CK 3 ) 2 IT(CH 2 ) 2 N(CH 5 ) 2 -2A1(C 2 H 5 ) 5 Bruser, Thiele, and Kuller have synthesized 1:1 addition complexes of a, a' -dipyridyl and 1,10-phenanthrolene with trimethyland trie thyl aluminum (15). They did not claim that the aluminum is pentacoordinate in these complexes. However, Dr. Thiele has indicated this in a private communication with the author. A1 2 (C 2 H 5 ) 6 + 2 P V/ \\ 2// \W/ M. A 1(C 2 H 5 ) 3 The interaction of tetramethyltetrazene with trimethyl aluminum has been shown to yield the 1:1 adduct, (CH,)pNN = NN(CH^) 2 'Al(C 2 Ht-)z, which decomposes unless it is stored at temperatures of -10° or lower (17). In the previous discussion concerning aluminum phosphorus compounds it was noted that tetraphenylbiphosphine reacts with trie thyl aluminum to form the 1:1 adduct (12). This is the only literature reference to this type reaction. \

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EXPERIMENTAL The manipulation of reagents All organo-aluminum compounds were handled either in a dry box (D. L. Herring Dri-Lab and Dri-Train combination), in an atmosphere of nitrogen, or in the glass vacuum line shown in Figure 1. Oxygen and moisture were rigorously excluded from all operations. Before reaction, all materials were degassed by freezing with liquid nitrogen, evacuating the reaction flask, closing the manifold stopcock, and allowing the material to warm to ambient temperature, this operation being carried out three times. In those reactions in which ethane was a product the liberated ethane was collected, purified, identified by its vapor pressure at -126.3° and -111.6° (literature (18) 55mm; 178mm), and its volume was measured. Materials Solvents were dried by distillation over calcium hydride and then stored over the same reagent. Triethylaluminum obtained from the Ethyl Corporation was fractionally distilled and the fraction boiling at 56° (0.5mm) was used. The preparation of the aminophosphines and the biphosphines used in this work is discussed in Part II. \

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• .Tr = 03 : i i h0

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8 Analyses Elemental analyses were done by the Schwarzkopf Microanalytical Laboratory. Melting points were obtained in sealed capillary tubes in a Thomas-Hoover capillary melting point apparatus and are uncorrected. Molecular weights were determined cryoscopically in benzene. An attempt to use a vapor-pressure osmometer was unsuccessful because the compounds decomposed in the short time they were in the instrument. A standard freezing point apparatus was modified to provide a slow nitrogen flush so that contact of the solution with the atmosphere could be minimized. The molecular weights reported are not very accurate. The values are generally low indicating that the compounds may have partially hydrolyzed despite all the precautions taken to exclude moisture from the cryoscopic systems. Infrared spectra The infrared spectra were recorded on a Perkin-Elmer Model 137 spectrometer using sodium chloride optics. The spectra of the solids were obtained from Nujol mulls. In all cases the samples were prepared in the dry box and stored under nitrogen until being placed in the instrument. A summary of the infrared data is found in Table 1.

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TA3LE 1 ssorptio: (PART I)* INFRARED ABSORPTION IN CX.' 1 3080(sh,s), 29&0(vs), 1950(vw) , 1890(vw), 1810(vw), 1580(vw), rr tt >i Airr tt ^ vCr f ^ 1 WO(sh,s), 1460(vs), WO(s), LC 3 H ? xT A1CC 2 H 5 ; 2 PCC 6 H 5 ; 2 J 3 i^QOCm), 1380(vs), 1310(w), 1220(w), 1190(w), 1170(ra), nujol 1120(s), 1100(s), 1070(w), 1020(m), lOOO(vs), 978(vs), 953(s), 935(m), 896(vs), 843(vs), 7^3(sh,vs), 7^0(vs) > 693(vs). 3«-20(m), 3120(s), 3020(s), 1969(w), 1890(w), 1820(w), 1660(w), 1590(m), 1490(s), C 7 Z n M&( k C e E c ) WO(s), lW(vs), 1400(sh,s), 5 / ° ^ 2 1380(s), 1370(s), 1330(m), neat 1310(m) , 1270(w), 1170(vs), 1140(vs), llOO(vs), 1070(m), 1030(s), 1010(sh,vs), 998(vs), 916(w), 868(s), 800(m,b), 7^9(sh,vs), 7^2(vs), 696(vs,b). 29^0(vs), 2150(vw), 1790(w,b), 1460(vs), 1410(vs), 1390(sh,vs), AloCCoHc)-. 1380(sh,s), 1330(sh,m,b), 2250 1230(s), I210(sh,s), 1190(s), neat 1100(m) , 1060(m), 988(vs,b), 955(vs), 901(s), 869(m,b), 7^6(s,b). 3^60(m), 3130(s), 2970(vs), 2840(sh,s), 1970(vw), 1900(vw), C / ,H Q NHP(CcHc) 5 'Al(CpHc) 3 ; 1820(vw), 1660(vw), 1590(w), 49 652 2 ? ^ I570(sh,vw), 1^90(s), l^-70(s), neat l^O(vs), 1410(s), 1370(vs), 1310(w), 1220(vs), 1200(vs), 1190(sh,s), 1160(sh.w), 1120(sh,w), llOO(vs), 1070(m), 1040(sh,m), 1030(s), 1010(vs), 998(vs), 990(sh,vs,b), 951(vs), 922(m), 855(sh,w,b), 840(m,b), 778(w), 7^6(vs), 732(vs), 69^ (vs). s, Strong; m, medium; w, weak; sh, shoulder; d, doublet; b, broad.

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10 Table 1 Cont'd. 3420(w), 3110(s), 3010(vs), 2920(sh,s), 1950(w), 1830(w) , 1810(w), 166C(w), 1580(d), 1570(sh,w), WO(vs), C 4 H q NHP(C fi H e -) 2 1460(sh,s), 1430(vs), 7 1390(sh,m), 1360(vs), 1320(w) , neat 1300(111), 1270(d), 1220(vs), 1200(sh,s), 1180(sh,d), 1150(w), 1090(s), 1070(d), 1030(s), 980(vs,b), 916(w,b), 837(s,b), 7^S(sb,vs,b), 732(vs), 695(vs). 3110(sh,s), 2950(vs), 1970(vw), 1900(vw), 1820(vw), 15S0(vw), 1460(vs), 1440(vs), 1410(d), C z ,H Q N[Al(C P H c .)p]P(C fi H [ .) 9 1390(sh,s), 1370(vs), 1360(s), * * y d ° p * 1310(w), I220(m), 1210(sh,d), nujol 1180(s), 1160(sh,d), 1090(s), 1080(sh,w), 1040(s), 1030(d), 982(vs), 959(s), 924(d), 855(vs), 847(sh,vs), 975(s), 739(vs), 70S(m), 696(vs). 2940(vs), 2840(s), 1470(sh,d), 1460(s), 1420(s), 1410(s), (CE,) ? NP(CK,)p-Al(CpH [ ,), 1370(d), 1300(s), 1280(s), * ° * * y ° 1270(d), 1230(s), 1180(vs > ), neat 1170(sh,m) , 1140(vw) , 1120(s), 1060(s), 1040(s), 1020(d), 980(vs), 945(vs), 902(vs), 851(s), 826(w), 7^5(w), 708(s,b) 3030(vs), 2960(vs), 2900(sh,vs), 2840(vs), 1470(sh,s), 1450(s), (CH,)pNP(CH,) p 1430(s), 1420(sh,d), 1290(s), D p 1270(s), 1190(vs), 1140(d), neat 1100(vw), 1060(s), 971(vs), 936(vs), 889(vs), 845(s), 811(m), 692(s). 3130(s), 2870(vs), 1970(w) , 1890(w), 1820(v), 1770(vw), (C H c -) NP(C £ -Kc) Al(CpH t -) H 1660(w) , 1590(d), 1490(s), d ? d b ? d d > d 1470(vs), 1410(s), 1380(vs), neat 1330(d), 1310(sh,m), 1290(s), 1230(d), 1200(vs), 1180(vs), 1100(vs), 1070(s), 1060(s), 1030(vs), 1000(s), 930(sh,s), 950(sh,s), 939(s), 926(s), 849(v), 794(s), 746(vs,b), 696(vs,b).

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11 Table 1 Cont * d . 5100 ( C 2 H 5 ^ 2^ ^ ^6" 5 ^ 2 neat (CH 5 ) 2 P?(CH 3 ) 2 -2A1(C 2 H $ ) $ neat (CH 3 ) 2 ?P(CH 3 ) 2 neat (C 6 H 5 ) 2 PP(C 6 H 5 ) 2 -A1(C 2 H 5 ) 3 nujol (C 6 H 5 ) 2 PP(C 6 H 5 ) 2 nujol C 2 H 5 N[P(C 6 H 3 ) 2 ] 2 -A1(C 2 H 5 ) 3 nujol ^xww(s) 1950(w) 1760(vw 1470(vs 1370(vs 1300(sh 1180(vs 1070(s) 998(s), 7^(vs; 2910(vs 1360(m) 1170(a) 909(sh, 821 (w,b 676(s,b 3020(s) l^-30(vs 887(vs) 3130(sh 1890(vw 1580(w) 14-30(vs 1300(m) 1160(m) 1090(s) 1000(s) 984(w,b 715(s), 3110 (sb 1970 (vw 1660(vw 1460(vs 1380(s) 1180(m) I090(s) 980(m,b 884(s,b 7^3(vs) 2990(vs), 2900(sh,s), 1880(w), 1810(w), , 1650(w), 1580(m), , 1460(s), 1430(vs), , 1340(m), 1320(sh,m), m), 1290(s), 1190(sb,vs), , 1160(sh,m), 1090(vs), 1060(sh,s), 1020(vs), 923(vs), 849(w), 790(s), 696(vs,b). , 1450(vs), 1410(vs), 1280(m), 1220(m), 980(vs,b), 9^3(vs), ,b), 889(sh,vs), 881(vs), , 734(m,b), 699(sh,w,b), 29^0(s), 2360(m), , 1290(s), 9^6(vs), 871(vs), 81500, 708(vs) 3110(sh,s), 2370(vs), 2840(sh,s), 1970(w), 1900(w), 1820(w), 1660(w), 1580(m), 1^70(sb,s), 1460(vs), 1^30(vs), 1400(a), 1370(s), 1330(a), 1310(m), 1270(w), 1220(w). 1170(d,vs), 1110(s), 1090(vs), 1070(m), 1020(m), 998(s), 982(s), 9^5(m) , 924(sh,m), 916(a), 844(vw ? b), 7^2 (vs), 718(s), 692(vs,b). s), 2980(vs), 1960(vw), , 1820(vw), 1660(vw), 1560(w), 14?0(vs), , 1380(s), 1320(w), 1200(sh,m), 1180(vs), 1120(a), 1110(s), 1070(s), 1030(a), , 9^8(v,b), 922(w), ), 971(s) ? 970(vs), 693(vs,b). ,s), 2960(vs), 2840(sh,s), ), 1900(vw), 1820(vw), ), 1590(vw), 1470(sh,s), ), 1430(vs), 1400(a), , 1310(a), 1230(w), , 1130(s), 1100(s), , 1060(s), 1030(m), ), 948(a), 921 (dm), ), 974(s), 972(sh,s), , 700(vs,b).

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12 Table 1 Cont'd. 5110(sh,m), 2950(vs), 2900(sh,vs), 1970(vw), 1890(vw) , C 2 H £ -N[P(C fi H ( -)p3p 1820(vw), 1590(w), 1460(s), ? P 1^30(s). 1370(s), 1300(w), nujol 1180(vw), llpO(m), 1090(s), 1060(s), 1030(m), 99S(w), 966(w), 924(n), 879(s), 854(w), 766(111), 7^9(s), 7^2(s), 73S(sh,s), 695(b,s). 3120(sh,s), 2960(vs), 1970(w), 1890(w), 1820(w), 1590(w), CH,NCP(C fi H c .)p]p.Al(CpH-), 1480(s), 1460(s), 1430(vs), y o p * * ^ p 2 1400 (m), 1370(m), 1300(w) , nujol 1220(w), 1180(m), 1160(sh,w), 1100(vs), 1080(vs), 1070(s), 1030(w), 995(sh,m), 987(m), 969(m). 9^8(m), 916(w,b), 866(vs), 747(vs), 698(vs). 3110(sh,vs), 2990(vs), 1960(vw) , CH : ,N[P(C f -H c -)p3p 1890(vw), 1820(vw), 1650(vw), ? P lp80(m), WO(vs), 14$0(vs), nujol 1420(sh,m), 1380(s), 1310(m), 1270(111), 1170(m), 1160(sh,m), 1090(vs), 1070(vs), 1020(m), 998(m), 966(vw), 917(d,w), 851(vs), 743(vs), 695(vs). 3110(sh,m), 2990(vs), 2900(sh,vs), 1970(vw), 1900(vw), 1820(vw), C(CpH c -)pAlN[P(C fi H c -)p]p]p 1590(w), 1470(sh,m), 1460(vs), <_p '(s), 1380(s), 1310(vw), nujol 1230(w), 1180(w,b), 1160(w), 1100(s), 1070(w), 1030(w), 1000(m), 938(sh,w), 964(w), 924(m), 901(vs), 810(s), 792(vs), 752(sh,ni), 741(vs), 704(sh,s), 694(vs). 3250(m), 3080(sh,m), 2960(vs), 2880(sh,s), 1960(vw), 1890(vw), HNCP(C f -H c -)p]p 1810(vw), 1480(sh,s), 14S0(s), y 1430(s), 1380(s), 1300(w0, nujol 1270(w), 12pO(m), 1160(vw,b), 1100(s), 1070(sh,w), 1020(m), 997(w). 916(sh,m), 905(sh,s), 897(vs), 79
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13 Nuclear magnetic resonance soectra •Tuclear magnetic resonance spectra were obtained using a Varian high resolution spectrometer, Model V-4-300-2, equipped with field homogeneity control, magnet insulation, and field stabilizer. The shift values were obtained by sweeping through the field slowly and interchanging a reference sample and the sample being studied. In this work acetaldehyde was used as the reference sample. The method produces the sample peaks and the acetaldehyde peaks on the same spectrum and from this the chemical shifts may be calculated in approximate T values. The shift of the phenyl protons is measured from the highest peak. Phosphoric acid (85 per cent) was used as an external standard for measuring the * P chemical shifts. The H spectra were determined at 56.4 He; the * P spectra, at 19.3 He. A summary of the nuclear magnetic resonance data is found in Table 2. T he interaction of isor>rot>ylaminodiphenylphosr>hine with triethyl aluminum 6(CH 3 ) 2 CHNHP(C 6 H 5 ) 2 + 3^ 2 ^ C 2 E ^e " 2[(CH 3 ) 2 CHN{A1(C 2 H 5 ) 2 ^P(C 6 H 5 ) 2 ] 5 + 6C 2 H & In a typical experiment a 1.68 gram (0.0146 mole) sample of triethyl aluminum was placed in a 100 ml, 2 neck reaction flask containing a teflon coated magnetic stirring

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14TA3L3 2 INFRARED ABSORPTION ASSIGNMENTS Grout) Range in cm. -l NHp ::h N=H Phenyl CH, CH 2 P-K Phenyl Al-H Phenyl NH 2 P-phenyl CH 2 C-CH $ C-(CH $ ) 5 C-CK 3 C-CH 5 C-(CH,), ?-CK 5 (CH 5 ) 2 NP (C 2 H 5 ) 2 N? Stretching absorptions (2 bands) Stretching absorptions (1 band) Stretching absorptions (1 band) C-H stretching absorption C-E stretching absorption C-H stretching absorption Phosphorus-hydrogen bond C-H stretching absorption Aluminum-hydrogen bond C=C in-plane vibrations NH deformation Phosphorus-carbon bond CH deformation CH deformation CH deformation CH deformation CH deformation OH deformation phosphorus-carbon bond Nitrogen-phosphorus bond CN vibrations in aliphatic amines Nitrogen-phosphorus bond 3500-3300 (

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15 Table 2 Cont'd. C-rouo Hanre in cm.** (CrOpN? Nitrogenphosphorus bond 1190 (s) (CoHjOpNP Nitrogen-phosphorus bond 1175 (m) (CH,)pNP Nitrogen-phosphorus bond 1064 (s) P-phenyl Phosphorus-carbon bond 1005995 (ra) PN PIT stretching absorption 7^0700 (s) CH Out-of-plane deformation (monosubstituted benzene) 710690 (s) All assignments except the PIT assignments are taken from Bellamy (22).

PAGE 25

16 bar. Three and fifty-four hundredths grams (0.0146 mole) of isopropylaminodiphenylphosphine was placed in a tipping tube and attached to the reaction flask. A vacuum stopcock was fitted into the other neck of the reaction flask and the entire apparatus was attached to the vacuum line. After degassing the reactants the isopropylaminodiphenylphosphine was added to the reaction flask which was cooled with liquid nitrogen. The reaction flask was allowed to warm slowly to room temperature during which time a gas was slowly evolved. The reaction flask was then heated for 40 hours at 50-55° to insure completion of the reaction. Fractional condensation yielded 0.0127 mole of ethane. The apparatus was then transferred to the dry box and the white solid material was recrystallized from hot hexane. This material heated at 189° with decomposition. The yield based on ethane elimination was 87 per cent. The infrared spectrum, Figure 2, of the solid product shows a strong peak at 1120 cm. which is associated with a tetracoordinate phosphorus atom having a P-phenyl bond (19). For comparison, Figures 3 and 4 show the infrared spectra of isopropylaminodiphenylphosphine and t ri ethyl aluminum, respectively. Anal . Calcd. for [(CH,) 2 CHN{A1(C 2 H 5 ) 2 "$P(C 6 H 5 ) 2 ] 5 : C, 69.71; H, 8.31; N, 4.28; P, 9.46; mol. wt. , 982. Found: C, 69.50; H, 8.07; N, 4.49; P, 9.18; mol. wt. , 983.

PAGE 26

INT ? 17 i — i CM LA W O , I C\J w OJ O w o OJ /">» W O O I f4 -P O a> W -d f-l s a i P-4

PAGE 27

18 LA w O w o CM W O o o
PAGE 28

19 1 v£> W CO o V-V CO rH < O a u -p o
PAGE 29

20 The proton nuclear magnetic resonance spectrum, Figure 5, is in accord with the formula hut can not he used to determine the polymeric nature of the material. This spectrum was ohtained from a sample of material dissolved in benzene so the chemical shift value of the phenyl group was not ohtained. The peak labeled A is difficult to see at this sweep rate; however, with a slow sweep rate and high resolution the peak is plainly a heptet. This is expected for the CH peak because the proton is coupled with the protons of the two adjacent methyl groups. The peak labeled B arises from the various methyl groups. The methyls of the ethyl groups form a triplet because the methyl protons are coupled with the methylene protons. Thistriplet has a doublet superimposed on it by the isopropyl methyl protons. This doublet arises from the methyl protons coupling with the single proton on the adjacent carbon atom. The C peak is an unsymmetrical quartet brought about by the methylene protons of the ethyl group coupling with the methyl protons. The interaction of tertiarybutylaminodiphenylphosphine with trie thy 1 aluminum 2(CH 3 ) 3 CNHP(C 6 H 5 ) 2 + A1 2 (C 2 H 5 ) 6 -* 2(CH $ ) 5 CNHP(C 6 H 5 ) 2 .A1(C 2 H 5 ) 3 By the vacuum method outlined above 5.06 grams (0.0197 mole) of tertiarybutylaminodiphenylphosphine was

PAGE 30

I — I OJ UN K O OJ LA w OJ O 21 W O OJ w O O 6 fH -P O o CO a> o o CO <1) o •H -P d hO cd S a 0) 0) h d O 0) fe d •H

PAGE 31

22 combined with. 2.24 grams (0.0190 mole) of tri ethyl aluminum using 10 ml of toluene as the solvent. The aminophosphine was slowly added to the reaction flask which was cooled by a dry ice-acetone bath. The reaction mixture was stirred at -78° for an hour and then allowed to warm to room temperature and stirred for an additional hour. The solvent was then removed under vacuum and the reaction product was transferred to the dry box. Heating the reaction product above room temperature caused immediate evolution of ethane. The infrared spectrum, Figure 6, of the molecular addition product clearly shows the NH stretching absorption at 3^60 cm." . The peak at 1120 cm." associated with tetracoordinate phosphorus having a P-phenyl bond is missing from this spectrum. Figure 7 shows, for comparison, the infrared spectrum of the starting material tertiarybutyl aminodiphenylphosphine . Anal . Calcd. for (CH^CNHPCCgH^AlCC^)^: C, 71.1$; H, 9.50; N, 3.77; P, 8.34; Al, 7.76; mol. wt., 371. Found: C, 71.16; H, 9.60; N, 3.79; P, 8.29; Al, 7.21; mol. wt., 412. The proton nuclear magnetic resonance spectrum of this compound, Figure 8, was obtained from a pure sample sealed in a glass tube. The peak labeled A is attributed to the phenyl protons. Peak B arises from the NH proton.

PAGE 32

25 lA W (\J O rH ««; *C\J l/V W O ^ PL, o W o O a d -p o 0) ft w •d .
PAGE 33

24 oj ^\ ITS W » Pk w o W o O e -P o W H faO •H

PAGE 34

fA LA w CM O 25 -3j CM LA w O CM O rA /—> rA W O O a -p o CD ft CO o ti a o CO cd fH O H -P CD a ctf a fH Ctf CD rH o -i I I « CO •H

PAGE 35

26 Peak G is attributed to both the tertiarybutyl methyl protons and to the methyl protons of the ethyl groups. Thus, peak C results from the superposition of the singlet peak from the tertiarybutyl methyl protons and the triplet peak from the ethyl methyl protons. Peak D is the quartet from the methylene protons coupling with the methyl protons. The pyrolysis of (CH^)^CEHP(C 6 H 5 ) 2 'A1(C 2 H 5 ) 3 (ch 3 ) 3 c:;h?(c 6 h 5 ) 2 'A1(c 2 h 5 ) $ (ch 3 ) 3 cn[ai(c 2 h 5 ) 2 ]p(c 6 h 5 ) 2 + C 2 H 6 A 5.26 gram (0.014 mole) sample of the adduct of aluminum triethyl and t-butylaminodiphenylphosphine was placed in a 25 ml reaction flask containing a magnetic stirring bar. The flask was fitted with a vacuum stopcock, attached to the vacuum line, and warmed (60-80°) for 18 hours. The total amount of ethane evolved was 0.0156 mole or 96 per cent of theory based on the above equation. The light brown solid reaction product was transferred to the dry box and recrystallized twice from benzene to yield a white crystalline solid melting at 166-167° with gas evolution. The infrared spectrum of this product, Figure 9? does not show the tetracoordinate phosphorus peak at 1120 cm." 1 . (The compound [(CH 3 ) 2 CHn{a1(C 2 H 5 ) 2 ^P(C & H 5 ) 2 ] 3 does show the peak at 1120 cm." .) Anal. Calcd. for (CH,) 5 C!T[Al(C 2 Hc) 2 ]P(C 6 H 5 ) 2 : C, 70.55; H, 8.56; N, 4.10; P, 9.07; Al , 7.90; mol. wt.,

PAGE 36

27 CM w vD O r— (^ CO lA W OJ o o W O O e u -p o (1) Pi to >d Q) & d M I I * ON bO •H

PAGE 37

28 34-1. Found: C, 70.25; H, 8.58; N, 4-. 24-; P, 8.89; Al , 7.86; mol. wt., 520. The proton nuclear magnetic reasonance spectrum, Figure 10, was determined from a sample dissolved in deuterated chloroform and sealed in a glass tube. Peaks A and A' are assigned to the phenyl protons. The orthoprotons of the benzene ring are sometimes shifted down field when the aromatic ring is attached to various substituents. Therefore, these two peaks don't necessarily mean that there are two types of phenyl groups present. Peak B is attributed to all the methyl protons. This peak is seen to result from the superposition of the singlet peak from the tertiarybutyl methyl protons and the triplet from the ethyl methyl protons. Peak C is a quartet arising from the methylene protons of the ethyl groups. The interaction of dimethylaminodimethylphosphine with trie thyl aluminum 2(CH 3 ) 2 NP(CH 3 ) 2 + A1 2 (C 2 H 5 ) 6 2(CH $ ) 2 N?(CH 5 ) 2 . Al(C 2 H 5 ) 5 By the vacuum method described previously 4. 06 grams (0.0586 mole) of dimethylaminodimethylphosphine was added to 4.4-1 grams (0.0586 mole) of trie thyl aluminum in 5 ml of toluene at -196°. The mixture was allowed to warm slowly to -78° at which temperature it was stirred for an hour. Vacuum distillation of the light brown solution (dimethylar:.inodimethylphosphine and the reaction product both attack

PAGE 38

29 m CO W O o <— t CM LA w o is o W O O rH -P o (D w o a a o 0) rH O •H -P CD d to a Fh d o O la rH o rH faO •H P-4

PAGE 39

30 most stopcock greases to form a black product) yielded 5.79 grams of a colorless liquid boiling at 80.5° (0.05mm). This corresponds to a yield of 68 per cent of theory based on the above equation. The infrared spectrum of the product is shown in Figure 11. Figure 12 shows, for comparison, the infrared spectrum of the starting material, dimethylaminodimethylphosphine. Anal. Calcd. for (CH 5 ) 2 N?(CH 5 ) 2 -Al(C 2 H 5 ),: C, 54.77; H, 12.41; N, 6.59; P, 14.1$; Al , 12.30; mol. wt., 219. Found: C, 54.53; H, 12.07; N, 6.29; P, 14.11; Al , 12.59; mol. wt., 213. The proton nuclear magnetic resonance spectru . of (CH 5 ) 2 NP(CH,) 2 -A1(C 2 H 5 ) 5 is found in Figure 13. This spectrum shows three main peaks, A, B, and C, which are attributed to the protons of the methyl groups on nitrogen, the protons of the methyl groups on phosphorus plus the protons of the ethyl methyl groups, and the methylene protons, respectively. This spectrum is interesting because it shows the splitting of the methyl protons that is brought about by their coupling with the phosphorus atom. It is noteworthy that the methyl groups on nitrogen are also coupled with the phosphorus atom. Peak A results from a singlet peak being superimposed on a doublet. This singlet peak is referred to as an extraneous peak because it doesn't

PAGE 40

31 LA W CM O *C\I W O Oh W O O a 3 & -p o 0) Q, to -d & d H I I

PAGE 41

32 CM W O Ph |Z! OJ W O o e o o ft CQ 13)
PAGE 42

00 o OJ rA <• c -C
PAGE 43

34 seem to belong to this molecule. This matter will be discussed later. Peak B is the doublet of the phosphorus methyl groups superimposed on the triplet of the ethyl methyls. Careful examination of this portion of the spectrum shows a small concentration of a second doublet for the phosphorus methyl protons. Peak C arises from the methylene protons. This peak appears to be a quintet rather than the normal quartet. This could be caused by coupling with the phosphorus atom but this is uncertain. Figure 14 shows the nuclear magnetic resonance spectrum of another sample of the above reaction product that was heated to 50° for 24hours during the synthesis. In peak A we note that the extraneous singlet peak is now the major peak. Peak 3 contains two doublets for the methyl groups on phosphorus and these are of about the same concentration. 51 The ^ ? chemical shifts are rather important in this case because large changes are noted. The phosphorus shifts for dimethylaminodimethylphosphine, the 1:1 unheated adduct with trie thy 1 aluminum, and the heated adduct are: -38.5, +4-0.5, and -35.5 ppm. relative to H^PO^. A sample of the molecular addition compound was heated to 65° on an oil bath in the dry box and held at that temperature for 60 hours. The resulting compound was analyzed and the n.m.r. and infrared spectra were obtained.

PAGE 44

55 w o < « ru W O ^s CM W O ch o a 3 *H -P o Q< CO d 0) -p h0 ,d cti d -d cd ,d ,d o ,d 5 •H

PAGE 45

36 These data indicate that the product contains two ethyl groups on the aluminum atom, two methyl groups on the phosphorus atom, and two methyl groups on the nitrogen atom. This material was vacuum distilled in order to purify the product but the compound decomposed with the evolution of a large amount of a volatile gas which was not identified. After distillation the analysis gave an approximate formula which was confirmed by n.m.r. as being (CH 3 ) 2 NA1(C 2 H 5 ) 2 . The reaction of trie thyl aluminum with dime thyl aminodimethylphosphine in a 2:1 molar ratio produced a material in small yield which, after being distilled twice, had an approximate analysis and molecular weight for the 2:1 adduct. This material could not be purified by distillation, however. The interaction of diethylaminodiphenylphosphine with trie thyl aluminum 2(C 2 H 5 ) 2 NP(C 6 H 5 ) 9 + A1 2 (C 2 H 5 ) 6 C 2 H 5 + other CH compounds + 2(c 2 h 5 ) 2 :t?(c 6 h 5 ) 2 ai(c 2 h 5 ) 2 h By the vacuum method 9.37 grams (0.03&4 mole) of diethylaminodiphenylphosphine was combined with 4-. 16 grams (0.0364 mole) of triethylaluminum at liquid nitrogen temperature. The reaction mixture was allowed to warm slowly to room temperature and was then stirred for an hour. During this time gas was evolved and the reaction

PAGE 46

57 at brown. The product was t: 'erred to a di Illation apparatus, re: . to the vacuum line, 7ield 10.3 b~' ^a colorleas liquid boil: >° (2. . .. . . . 3d or. the above . . r cent. 2:. es collected during the distillation j fractionated but the only product identified was C.CC15 moles of ethylene. infrar . I sctrum of this product (C 9 H^) X?(C.-Hr-)p 2"5 y 2 shown in ?!~ure 15. laic spectra::: should be red with the spectrum of die:, Lphenyl Lne, are 16, in order to see that all of the origin; iks are still present. This would indicate that the aminoill intact:, bo peak ia noted in r... or Ain re a. on oi .a c ctrum. b "pi. ' : .10; ::, < . : , .02; Ai , 7.86; mol. at., j bound: C, 70.1b; H, 8.95; N, 4.11; ?, 9.07; Ai , 7.61; mol. wt. , .. roton nucle . ;trum, >ws the two ethyl . nitre .torn, h nyl ;r d torn, '. 2 two s on . om. • of protons c. Peak A arj phenyl -aoup. Peak 3 i . . irtet an:

PAGE 47

38 w oj LA W o -a! OJ LA « O OJ lA w OJ o o £3 3 -P o Q) ft W d 0) cm d M I l A •H

PAGE 48

39 w v.0 O ! gs CO w cm o O -P o W T) U H I I •H P4

PAGE 49

40 w (\J w O H CM lA W o
PAGE 50

41 methylene protons of the nitrogen ethyl group. Peak C is attributed to two triplet peaks from the methyl protons of the two different types of ethyl groups present. Peak D is the normal quartet arising from the protons of the methylene group attached to aluminum. This spectrum gives no evidence for a single hydrogen atom being present. If there is no single hydrogen atom present and the compound is monomeric then the compound would have an unpaired electron. The magnetic moment of a sample of this compound was measured on the Gouy balance and it was determined that it is diamagnetic, therefore there are no unpaired electrons present. This fact was confirmed by obtaining the electron spin resonance spectrum which contained no peaks indicating no unpaired electrons are present. The interaction of tetramethylbiohosohine with triethylaluminum (CH 5 ) 2 ??(CH 5 ) 2 + A1 2 (C 2 H 5 ) 6 -* (CH 3 ) 2 PP(CE $ ) 2 .2A1(C 2 H 5 ) 3 By the vacuum method an excess of tetramethylbiphosphine was condensed onto 1.63 grams (0.014-3 mole) of trie thyl aluminum at liquid nitrogen temperature. The reaction mixture was allowed to warm slox^ly to room temperature and was then stirred for an hour. The excess biphosphine was removed under vacuum and the liquid product was stirred for an additional 12 hours at room temperature.

PAGE 51

4-2 Distillation yielded 1.54grams of a colorless liquid which boils at 102° (0.15mm), 66 per cent of theory according to the above equation. The infrared spectrum of this product is found in Figure 18. Figure 19 is the infrared spectrum of tetramethylbiphosphine . Anal . Calcd. for (CH^) 2 ?P(CH 3 ) 2 *2A1(C 2 H 5 ) 5 : C, 54.84; E, 12.08; P, 17.68; Al , 15-40; mol. wt., 550. Found: C, 54.79; H, 12.26; P, 17.72; Al , 15.13; mol. wt., 292 (Rast method, 592). The proton nuclear magnetic resonance spectrum of this compound is found in Figure 20. This spectrum is composed of three peaks, A, 3, and C, which arise from the methyl groups on the phosphorus atom, the ethyl methyl groups, and the methyl groups. The triplet and quartet up field are typical of ethyl groups on aluminum. The tripling of the methyl protons on phosphorus arises from the protons coupling with both phosphorus atoms. The starting material, tetramethylbiphosphine, also shows this tripling of the methyl protons. An attempt to prepare the 1:1 molecular addition compound by reacting tetramethylbiphosphine and triethylaluminum in equimolar amounts was unsuccessful.

PAGE 52

^3 W CM O ; CM O >> > CM /-> W O f . O -O 03 Q< Cfl -tj 0) d H '. 1x4 ^. . .Ji i ii l . i Kn xtl . • «i«»»t*«***«**»i<«>"" »*-i i ' __ "

PAGE 53

44eg W o PL, PM
PAGE 54

45 w CO O H HI O O S D £-1 •P O CD ft W FQ O d o w 0) o •rH -P bO a o iH O .-I o CM 60

PAGE 55

The interaction of tetrauhenr/lbiphosphine with triethylaluminum * 2(C 6 H 5 ) 2 PP(C 6 H 5 ) 2 + A1 2 (C 2 H 5 ) 6 2(C 5 H 5 ) 2 ?P(C 6 H 5 ) 2 .A1(C 2 K 5 ) 5 By the vacuum method 2.26 grams (0.00610 mole) of tetraphenylbiphosphine was added to 1.41 grams (0.00123 mole) of triethylaluminum in 8 ml of toluene at -78°. The heterogeneous mixture was stirred at this temperature for an hour, and upon being allowed to warm slowly to room temperature a clear solution was obtained. The toluene was removed under vacuum and the remaining solid was transferred to the dry box and recrystallized from hot hexane. The yield was 1.80 grams of a white crystalline solid melting at 99-101° (61 per cent of theory according to the above equation). The infrared spectrum of this compound, Figure 21, does not show the peak at 1120 cm." for tetracoordinate phosphorus having a P-phenyl bond. Figure 22 is the infrared spectrum of the starting material, tetraphenylbiphosphine. This compound was reported in the literature after it had been synthesized in our laboratory (12). These authors were concerned with the order of organometallic reagents interacting with biphosphines to cleave the P— P bond. The bonding in the tetraphenylbiphosphine-triethylaluminum adduct was not considered, nor were spectral data reported. The adduct was characterized by phosphorus and aluminum analysis and the melting point.

PAGE 56

47 w CM O CM w O CM Ph CM •~n LTv W (D O o a •p o <1> p< ra
PAGE 57

48 CO o Ph W vD O O e -p o 0) ft w •d a CM OJ •H P<4

PAGE 58

4-9 Anal. Calcd. for (C 6 E-)p?P(C 6 Ec) 2 Al(C 2 E 5 ) 5 : C, 74.36; E, 7.23; P, 12.79; Al, 5.57; mol. wt., 485. Found: C, 71.02; H, 6.87; P, 12.4-0; Al , 5.58; mol . wt. , 464. The proton nuclear magnetic resonance spectrum for this adduct, Figure 23, consists of three peaks; a typical phenyl peak A, a triplet B, and quintet C. These peaks are assigned to the Phenyl protons, the methyl protons and the methylene protons, respectively. The quintet for the methylene protons probably arises from coupling with the phosphorus atom. This spectrum indicates that only one 31 type of phenyl group is present. The ^ P n.m.r. spectrum was obtained and it consisted of a single peak confirming the fact that the phosphorus atoms are equivalent. It should be noted that the molar ratio of triethylaluminum to tetraphenylbiphosphine was 2:1 in this experiment but the product obtained was the 1:1 adduct. This indicates that under these conditions the 1:1 adduct is the favored product. The interaction of bis(diphenylphosphino)ethylamine with tri ethyl aluminum 2C 2 E 5 N[P(C 6 E 5 ) 2 ] 2 + A1 2 (C 2 E 5 ) 6 2C 2 E 5 N[P(C 6 E 5 ) 2 ] 2 -A1(C 2 E 5 ) 3 By the vacuum method 4.04 grams (0.00977 mole) of bis(diphenylphosphino)ethylamine was added to 1.12 grams (0.00977 mole) of triethylaluminum in 5 ml of toluene at

PAGE 59

50 in CM o <3 CM w o Ph Ph CM lA W <£ O o s Fh •p o 0) ft w I I « CM 60 •H

PAGE 60

51 -73°.. The reaction mixture was stirred at this temperature for an hour and was then allowed to warm to room temperature and was stirred for an additional hour. The solvent was then removed under vacuum and the resulting material was transferred to the dry box where it was recrystallized repeatedly from hexane to remove the last traces of toluene. This procedure produced a 45 per cent yield (based on the above equation) of a white crystalline solid melting at 78-82°. The • .frared spectrum of this compound, Figure 24, does not show a peak at 1120 cm." as would be expected if the aluminum atom were bonded to only one of the phosphorus atoms. The infrared spectrum of bis(diphenylphosphino)ethylamine is shown in Figure 25. Anal . Calcd. for C 2 H 5 *7[P(C 6 H,-) 2 ] 2 'Al(C 2 Hc) 5 : C, 72.84; H, 7.64; N, 2.66; P, 11.74; Al , 5.11; mol . wt. , 528. Found: C, 75.07; H, 7.56; N, 2.87; P, 11.50; Al , 5.19; mol. wt. , 503. The proton nuclear magnetic resonance spectrum of this compound is found in Figure 26. The peak labeled A arises from the protons of the phenyl groups. The rather broad peak labeled B is attributed to the protons of the methylene group attached to nitrogen. The C peak arises from the methyl protons of the ethyl group on aluminum. The D peak is attributed to both the protons of the methylene

PAGE 61

52 LA W CM O < *CM I — I CM LA w O ft 1—1 !3 lA w CM O o I 3 Fh -p o (D ft CO •d CD .cd a CM •H ft

PAGE 62

53

PAGE 63

54 n o l-CN w CM O <$ CM r— i CM L!A w (X) o "^-^ fin i i UA CM O
PAGE 64

55 group on aluminum and to the protons of the methyl portion of the ethyl group on nitrogen. This is the only spectrum examined in this study that contains the ethyl triplet and quartet shifted down field so that the methyl of the nitrogen ethyl falls in the same general area as the methylene group attached to aluminum. This spectrum indicates that only one type of phenyl group is present and this implies that there is only one type of phosphorus 31 atom in the molecule. The ^P n.m.r. spectrum shows only one peak for phosphorus confirming the fact that the phosphorus atoms are equivalent. The interaction of bis(diphenylphosohino)methylamine with ri ethyl aluminum 2CH 3 N[P(C 6 H 5 ) 2 ] 2 + A1 2 (C 2 H 5 ) 6 2CH $ N[P(C 5 K 5 ) 2 ] 2 .A1(C 2 H 5 ) 5 By the vacuum method described previously 2.26 grams (0.00566 mole) of bis(diphenylphosphino)methylamine was added to 1.29 grams (0.0115 mole) of tri ethyl aluminum in 5 ml of toluene at -73°. The reaction mixture was stirred at this temperature for an hour and was then allowed to warm to room temperature and was stirred for an additional hour. The solvent was then removed under vacuum and the resulting crystals were transferred to the dry box. Recrystallization from hexane yielded 2.3 grams, 80 per cent of theory, of a white crystalline solid melting at 130-132°.

PAGE 65

56 Figure 27 shows the infrared spectrum of this compound and again we notice that the peak at 1120 cm." is missing. The infrared spectrum of bis(diphenylphosphino)methylamine is found in Figure 28. Anal. Calcd. for CH 5 N[P(C 6 H 5 ) 2 3 2 'A1(C 2 H 5 ) 5 : C, 72.4-9; H, 7.45; N, 2.73; ?, 12.05; Al , 5.25; mol. wt., 514. Found: C, 72.50; H, 7.43; N, 2.94; ?, 11.83; Al, 5.60; mol . wt . , 422 . The proton nuclear magnetic resonance spectrum is shown in Figure 29 and again v/e see that the phenyl groups are all equivalent. Peak A is attributed to the protons of the phenyl groups. Peak 3 is a triplet arising from the protons of the nitrogen methyl group coupling with the tv/o phosphorus atoms. Peaks C and D are the triplet and quartet peaks of the ethyl groups on aluminum. The phosphorus n.m.r. spectrum shows only one peak confirming the fact that both of the phosphorus atoms are equivalent. It is notable that the 2:1 molecular addition compound was not formed in this reaction. The interaction of bis(dinhenylohosphino) amine with triethyl aluminum 2HN[P(C 6 H 5 ) 2 ] 2 + A1 2 (C 2 H 5 ) 6 -2C 2 H 6 [(c 2 h 5 ) 2 ain{p(c 6 h 5 ) 2 } 2 ] 2 I'd.
PAGE 66

57 w C\J O CM i— i CO LA w O Ph i i m o «H O e 3 o 0 •H

PAGE 67

58 CM hO •H pq fl .
PAGE 68

LA « C\J O 59 o C\J I — I C\J LA O Ph W O en o (4 •p o 0) ft 03 CD O id o CO CD u o •H -P CD d fcO e Sh ctf CD H O [25 !x! ON CM •H

PAGE 69

60 (0.0123 dole) of trie thyl aluminum in 5 ml of toluene at -78°. The heterogeneous mixture was stirred at this temperature for an hour and was then allowed to warm slowly, At about -10° all the solid material dissolved in the pale yellow solution. Upon allowing the solution to warm to room temperature the evolution of gas commenced. Stirring at room temperature for four hours produced 0.004-9 moles of ethane gas. The reaction flask was then heated with a water bath to 50° for an hour, yielding a total of S3 per cent of the theoretical amount of ethane based on the above equation. After removal of the toluene the white crystalline solid was transferred to the dry box and analyzed without further purification. The yield was 5.5 grams (94 per cent) of a white crystalline solid melting with decomposition at 189°. The infrared spectrum, Figure 30, does not show a peak at 1120 cm." indicating that the normal tetracoordinate phosphorus having a P-phenyl bond is absent from the molecule. The infrared spectrum of HN[P(C r Hc) 2 ] 2 is found in Figure 31. Anal. Calcd. for [(C 2 H^) 2 A1N{P(C 6 H 5 ) 2 ^ 2 ] 2 : C, 71.63; H, 6.44; IT, 2.98; P, 13.20; Al , 5.75; mol. wt., 939. Found: C, 71.93; H, 6.67; N, 3.04; p, 12.91; Al, 5.88; mol. wt., 870.

PAGE 70

61 i — i OJ oj o p4 H CO lA w oj o Ch o p o c p, CO o c. r o bD f-q

PAGE 71

o o ; CO ...... ........... 62

PAGE 72

63 The nuclear magnetic resonance spectrum of this compound was not determined because the compound decomposes in deuterated chloroform. •Table 1 is a compilation of the infrared spectral data obtained in this study. The peak in the region of 1120 cm. has been assigned to a tetracoordinate phosphorus atom by Sheldon and Tyree (20). This assignment was modified by Hart and Sisler to limit it to a tetracoordinate phosphorus atom having a P-phenyl bond (19). Paciorek and Kratzer noted the formation of this peak but they attributed it to the formation of pentacovalent rather than tetracoordinate phosphorus (21). Table 2 is a compilation of the infrared assignments from Bellamy's book (22) on infrared spectra with the exception of the PIT assignments. It is difficult to make assignments for the PN absorptions because the range over which they occur is rather large. Mayhood and Harvey assign peaks in the region 730-704cm." to the PN stretch. The (CH-OpN-P group has several peaks assigned; 1316-12SO, 1190, and a peak at 1064 cm." which is characteristic for this group (23). Mclvor and Hubley have examined the (CpHcOp^-P group and noted the following joeaks: 1210, 1175* and the range 7^0-715 cm." 1 (24). Table 3 is a compilation of the nuclear magnetic resonance data obtained in this study. This table provides

PAGE 73

co w J < < O w o z o 00 w Pi CJ H w Pm z ^ o i Pi 3 1-1 y z w — 4-1 -I <4M C lo g g 0) 4-1 CO F. •H X o u c. a 4-1 en cj i-H < CO PS CJ o en PS 3T cj z CM co i CM i-M CM CM ^—s CO /-^ • o* -a* o *-* o s -' o m as CM 00 CO I • a" o ^ nO on CM CM I .-H VO » o o f-i o. t-i a. on
PAGE 74

CO w 5 0) 3 4J c o (0 . *J S B -tf P-nw C • O O •-I i-4 t-i o. Vj Cm CO X! • U-l CO w a. sc CJ co cj CM o * w 0) 3 i-H 03 > X o 1-1 a a < re cj CO Ph CJ 53 csi M + O c 3 O a. E o u oo » cr> cr oo cr oo • o r*
PAGE 75

66 examples of the relationship between the chemical shift value and the electronegativity of the atom to which the hydrogen atom is bonded. The basic observation is the fact that as the electronegativity, or the electron density is increased on the adjacent atom to which the hydrogen is bonded, the peak is shifted down field. Conversely, as the electron density on the adjacent atom is decreased, the peak is shifted up field. For instance, the peak for the methylene protons of an ethyl g iched to nitrogen atoms are down field while the peak for the protons of a methylene group attached to a carbon atom are up field. This effect is noticeable ov several bonds; for instance note the locations or shift values for the protons of: (a) a methylene group attached to nitrogen; (b) a methylene or a methyl group attached to carbon, and (c) a methylene group attached to aluminum. We find that: the peaks for the protons of the methylene groups attached to nitrogen, the most electronegative atom considered, lie furthest down field; the peaks for the protons of methylene or methyl groups attached to carbon lie up field from the nitrogen methylene groups; and the peaks for the protons of the methylene groups attached to aluminum, the most electropositive atom considered, lie furthest up field from the nitrogen methylene groups. The peaks for hydrogen atoms in aromatic ring systems usually lie down field beyond ie peaks for hydrogen atoms attached to nitrogen.

PAGE 76

67 The most noticeable shift is that of the methylene protons in the ethyl groups bonded to aluminum atoms. The normal ethyl pattern is a triplet for the methyl protons and a quartet for the methylene protons with the quartet peak lying down field from the triplet peak. Ve note, however, that the low electronegativity of the aluminum atom causes the pattern to be inverted, that is, the quartet peak is shifted up field from the triplet peak.

PAGE 77

DISCUSSIOIT AND CONCLUSIONS Studies with aluminum alkyls have shown that hydrocarbon elimination occurs when electron donors, such as amines or hydrazines, containing a hydrogen atom bonded to the nitrogen are reacted with aluminum alkyls. The reaction of triethyl aluminum with isopropylaminodiphenylphosphine yields a trimeric material, with the formula C(CH,) 2 CHN-(A1(C 2 H 5 ) 2 "}P(C 6 H 5 ) 2 ],, after undergoing ethane elimination. The trimeric nature of this compound appears to be similar to the known trimeric compound [H 2 AlP(C 2 Ht-) 2 ], (9) which exists in the form of a six-membered ring. The infrared spectrum of this aminophosphine derivative shows a peak at 1120 cm." which is assigned to a tetracoordinate phosphorus atom containing a P-phenyl bond (19). This infrared evidence indicates that the aluminum is bonded to the phosphorus as well as to the nitrogen atom and, therefore, this compound probably exists as a nine-membered ring as shown below: 68

PAGE 78

69 C, ?3 H 7 5 6 -4-C 2 H 5 | c 6 :-: 5 I 'A1 x C ".i-C^, C^HH \ H 7 C 3 Al. .K "?°2 J^P 3 7 6 ? The reaction of tertiarybutylaminodiphenylphosphine with tri ethyl aluminum yields the molecular addition compound at room temperature. This material is not stable above room temperature. It is interesting to note that this adduct does not show the peak at 1120 cm." in the infrared spectrum. This indicates that the normal tetracoordinate phosphorus is missing from this compound. It should be noted, however, that when tertiarybutylaminodiphenylphosphine is reacted with chloramine the resulting product is aminotertiarybutylaminodiphenylphosphonium chloride [t-C^HgHHPCCgH^gCHHg^Cl (19), indicating that the most basic site in the molecule is the phosphorus atom. If we accept this evidence that the most basic site in the aminophosphine molecule is the phosphorus atom then we would expect a strong Lewis acid such as triethylaluminum to react at the phosohorus atom.

PAGE 79

70 If we examine the infrared spectrum of the free base and compare the NH and p-phenyl absorptions with the same absorptions in the triethylaluminum adduct we note that the NH peak at 34-20 cm. in the free base is shifted to 3450 cn. _i in the adduct and the ?-phenyl peak at 14-30 cm." in the free base is shifted to 14-4-0 cm." in the adduct. Both groups seem to be affected by the presence of the triethylaluminum moiety. Bellamy (22) notes that as the polar character of a bond is decreased the vibrational frequency frequently rises. Both of the peaks mentioned have been shifted to shorter wavelength, or higher frequency, as compared with the peak in the pure aminophosphine. These facts, coupled with the fact that the peak for tetracoordinate phosphorus, at 1120 cm." in the infrared spectrum, is missing, leads one to consider the possibility of the aluminum forming a bond with both the nitrogen and the phosphorus atoms. If such is the case, the aluminum, nitrogen and phosphorus atoms form a threemembered ring and the normal peak for the tetracoordinate phosphorus atom containing a ?-phenyl bond may be shifted. The question might arise as to whether a tetracoordinate phosphorus atom having a ?-phenyl bond would be expected to show the peak at 1120 cm." in the infrared spectrum if an aluminum atom were bonded to it. Since the aluminum-phosphorus bond would reduce the electron density

PAGE 80

71 on the phosphorus atom one might argue that the normal peak for tetracoordinate phosphorus would be shifted by the presence of the aluminum atom. An answer to this argument is the fact that the compound C(GH^)pCH::^Al(C 2 K-) 5 }?(C^H,) 2 1* does show the normal peak for tetracoordinate phosphorus having a ?-phenyl bond at 1120 cm. . When tertiarybutylaminodiphenylphosphine-triethylaluminum is warmed above room temperature a slow evolution of ethane begins. After the gas evolution has ceased the resulting compound has the formula (CH^^CrTCAlCCpHOp^CC--— )?• This monomeric compound is in contrast to the trimeric ring compound formed from the reaction of isopropylaminodiphenvlphosphine with triethylaluminum. Another contrasting feature is the absence of the peak at 1120 cm." in the infrared spectrum. If we examine the P-phenyl absorption in this compound we see that it fails at 14-4-0 cm." as it does in the 1:1 adduct. This is not a large shift but it leads one to consider the possibility of the aluminum atom, which is already bonded to the nitrogen atom, also interacting with the phosphorus atom. If this situation does exist the strained bond angles might account for the absence of the normal tetracoordinate phosphorus peak. It was thought that the phosphorus nuclear magnetic resonance spectrum might help to clarify this point by showing the change in the phosphorus chemical shift between

PAGE 81

72 the free aminophosphine, the trie thy 1 aluminum adduct, and the resulting compound having aluminum bonded to nitrogen. However, upon examining all the evidence it was determined that the chemical shift values do not yield a clear verdict in this matter. After more examples are reported it might "be possible to make predictions but at present a definite trend is not observed. Polynuclear electron donor species such as aminophosphines, bis (phosphino) amines, and biphosphines that do not contain a hydrogen atom bonded to the basic atoms would be expected to react with tri ethyl aluminum to form a product containing an aluminum atom bonded to each basic site, provided the proper amount of trie thyl aluminum is used and steric interactions do not prohibit such bonding. In this study the only polynuclear base that reacted with triethylaluminum in this manner is tetramethylbiphosphine. ( Dimethyl aminodime thyl phosphine yielded a small amount of material that had the approximate composition for a 2:1 adduct but it could not be purified by distillation.) Burg (25) has shoxm that tetramethylbiphosphine reacts with diborane to form both the monoand the di-adducts, (CH-)o??(CH-,) 2 * 3H 3 and (CK,) 2 ??(CH 5 ) 2 -2BH 5 . This confirms the fact that both the phosphorus atoms in tetramethylbiphosphine have the ability to donate a pair of electrons to an electron acceptor. Garrett and Urry (26) have

PAGE 82

73 synthesized a molecular addition product with the formula (CH 5 ) 2 PP(CHj) 2 -B 2 Cl^. This provides another example of both phosphorus atoms acting as basic centers. In the light of these experiments it is interesting to note that when tetramethylbiphosphine is reacted with trie thyl aluminum the 1:1 reaction product could not be isolated under the conditions of our experiments. The interaction of triethyl aluminum with tetraphenylbiphosphine was studied in our laboratory just prior to a paper being published by Issleib and Krech (12) which describes the s3rnthesis of the 1:1 adduct. Since these authors did not consider the bonding in this molecule we are including all the information obtained in our study. The most important difference we note when comparing the tetramethylbiphosphine adduct with the tetraphenylbiphosphine adduct is the fact that tetramethylbiphosphine forms only a 2:1 addition compound whereas tetraphenylbiphosphine forms only the 1:1 addition compound. At first we are tempted to say that steric interactions prevent two triethyl aluminum groups from bonding to the biphosphine because of the size of the phenyl groups. An examination of a model of the tetraphenylbiphosphine-triethyl aluminum 1:1 adduct indicates, however, that there is room for another triethyl aluminum group. Another interesting fact is that the infrared soectrum of the 1:1 adduct does not

PAGE 83

74 contain the normal tetracoordinate phosphorus peak that we would expect to find if the aluminum were bonded to onlyone phosphorus atom. An examination of the proton nuclear magnetic resonance spectrum of the tetraphenylbiphosphine-triethylaluminum 1:1 adduct indicates that all the phenyl groups are equivalent. If the aluminum were bonded to only one of the phosphorus atoms, the phenyl groups attached to the phosphorus would be expected to show two peaks in the spectrum because the environment of the two phenyl groups attached to the quadruply bonded phosphorus should differ from that of the two attached to the triply bonded phosphorus. It has been pointed out previously (1), however, that there is an alternative to this explanation of the n.m.r. results. This alternative involves the very rapid transfer of alkylaluminum groups from one phosphorus atom to the other phosphorus atom in the biphosphine addition compound. If the rate at which such exchange occurs were greater than the frequency separation of the resonance peaks corresponding to the two environments of the phenyl groups, then the two peaks would merge into a single peak of intermediate chemical shift. In the case of the tetramethylhydrazine-triethylaluminum 1:1 adduct it was impossible to prove which situation really exists but in the case of the tetraphenylbiphosphine-triethylaluminum 1:1 adduct there are other

PAGE 84

75 tools available that have allowed us to resolve this question. The first of these tools is zhe J P nuclear magnetic resonance spectrum. (Our laboratory is not 14 equipped zo obtain the ^ N nuclear magnetic resonance spectrum.) The phosphorus n.m.r. spectrum of tetraphe— 1biphosphine-triethylaluminum contains only one peak indicating that there is only one type of phosphorus present. If the aluminum were bonding to first one phosphorus atom and then the other we would expect to see two peaks because the quadruply bonded phosphorus would have a different environment than the triply bonded phosphorus. The phosphorus n.m.r. carries more weight than the proton n.m.r. because in the case of the biphosphine "Che chemical shift of the phosphorus atoms is larger than the chemical shift of hydrogen atoms and, therefore, one might expect to see two peaks rather than one of intermediate chemical shift if the aluminum were rapidly bonding to first one phosphorus atom and then to the other. The existence of only one peak in the phosphorus n.m.r. indicates that both phosphorus atoms have the same environment and therefore the phosphorus atoms are symmetrically located with respect to the aluminum atom, and therefore the aluminum atom is pentacoordinate. The other tool we can utilize in determining the nature of the bonding in the tetraphenylbiphosphine-triethyl aluminum adduct is the infrared spectrum. It has been

PAGE 85

76 mentioned previously that a normal tetracoordinate phosphorus atom containing a P-phenyl "bond exhibits a peak in the infrared spectrum at about 1120 cm." . It has also been suggested that if a tricoordinate phosphorus atom became tetracoordinate through the formation of a small ring the resulting tetracoordinate phosphorus atom would not be expected to absorb infrared energy at the same frequency as a normal tetracoordinate phosphorus atom. If the trie thyl aluminum group were exchanging between the two phosphorus atoms in tetraphenylbiphosphine the infrared spectrum would show the normal peak associated with tetracoordinate phosphorus because infrared, unlike n.m.r., is a rapid experiment. Since there is no peak at 1120 cm." in the infrared spectrum this compound may be assumed not to contain the normal tetracoordinate phosphorus. In this case the combination of infrared and n.m.r. evidence seems to prove the pentacoordinate character of the aluminum atom because: First, the proton n.m.r. spectrum shows all the phenyl groups to be equivalent. 51 Second, the y P n.m.r. spectrum shows both the phosphorus atoms to be equivalent. Third, the infrared spectrum does not show a peak at 1120 cm. which is associated with the normal tetracoordinate phosphorus containing a P-phenyl bond.

PAGE 86

77 Therefore, considering these points we may conclude that the phosphorus atoms are symmetrically located with respect to the aluminum atom. This must be considered as proof of the pentacoordinate character of the aluminum atom. When a nitrogen atom is substituted for a phosphorus atom in tetramethylbiphosphine the resulting molecule is dimethylaminodimethylphosphine (27). The reactions of dime thylaminodimethylphosphine would be expected to be similar to the reactions of tetramethylbiphosphine due to structural similarities. Holmes and Wagner have shown that dimethylaminodimethylphosphine reacts with trimethyland triethylboron to form 1:1 adducts (28). It has also been shown that dimethylaminodimethylphosphine reacts with diborane to form both the 1:1 and the 1:2 adducts, (CH $ ) 2 i:?(CH 5 ) 2 -3H 3 and (CH 5 ) 2 NP(CH,) 2 '2BH 5 (29). In the work of Holmes and Wagner the reaction of trimethylboron v/ith dimethylaminodimethylphosphine also produced the products of cleaving the PIT bond, that is, (CH,) 2 NB(CH,) 2 + (CH,),P'B(CHZ ),. We have shown that tri ethyl aluminum 3 3 5 3 reacts with dimethylaminodimethylphosphine to form the 1:1 adduct and have indications that the 2:1 adduct might be formed. The proton n.m.r. for the 1:1 adduct with triethylaluminum, Figure 13, shows one extraneous peak in the region of the doublet peak assigned to the methyl groups attached

PAGE 87

7S to nitrogen. This spectrum should he compared with Figure 14which is the spectrum of a product synthesized by the same method except that the material \
PAGE 88

79 the phosphorus. This v. r ould account for the singlet peak referred to above as the extraneous peak. Roberts has pointed out that shift values can be utilized as a measure of electron density or electronegativity (30). The fact that the extraneous peak is shifted up field compared with the original doublet can be explained by the fact that the electron density on the nitrogen would be reduced by having an aluminum atom bonded to it. On the basis of the above discussion the 1:1 adduct is really a mixture which contains approximately 80 per cent of the aluminum atoms bonded to phosphorus and 20 per cent bonded to nitrogen. In order to determine the extent of this heat effect a sealed tube containing a sample of the unheated 1:1 adduct was heated to 70° for 50 hours. The n.m.r. spectrum of the sample was obtained at room temperature periodically during this 50-hour period. After 50 hours of heating the singlet peak had increased in size compared to the doublet peak to indicate a 95 per cent concentration of the material postulated to contain an aluminum-nitrogen bond. It is possible that the kinetics of the initial reaction favor formation of the phosphorus-aluminum bond but that the nitrogen aluminum bond is thermodynamic ally more stable. In any case, it is apparent that two products are being formed and that the product responsible for the anomolous peak is being generated as the mixture is heated.

PAGE 89

80 An attempt to produce a larger sample of the material presumed to contain an aluminum-nitrogen bond resulted in the pyrolysis of the 1:1 adduct. This was evidenced by the formation of a compound which n.m.r. and elemental analysis indicate is probably (CH-,) 2 ?[Ai(C 2 H,-) 2 3 IT (CH $ ) 2 . This formula leaves an unpaired electron in the molecule so it is thought that the compound is probably a dimer. This material was pyrolyzed further when distillation was attempted. The principal distillation product contains only a small amount of phosphorus. Elemental analysis and proton n.m.r. spectroscopy indicate that this material is impure dimethylaminodiethylalane, (CHOpNAlCCUHtOp. This product would be in accord with the reaction of dimethylaminodimethylphosphine with trimethylboron (28). (CH 3 ) 2 NP(CH 3 ) 2 + 23(CH 5 ) 3 (CH^ltfBCCH^ + (CH 3 ) 3 P.B(CH 3 ) 5 The interaction of diethylaminodiphenylphosphine with triethylaluminum is very interesting in as much as a simple molecular addition compound is not obtained. The reaction proceeds with the elimination of a mixture of hydrocarbon compounds, ethylene being the only one positively identified. The proton n.m.r. spectrum of the distilled product gives a great deal of information concerning what has taken place in the reaction. This

PAGE 90

81 spectrum indicates that there are two ethyl groups on the nitrogen atom, two ethyl groups on the aluminum atom, and two phenyl groups on the phosphorus atom. This indicates that aluminum has lost an ethyl group perhaps in a growth type reaction such as that shown by the following equations (3D: A1(C 2 H 5 ) 3 T HA1(C 2 H 5 ) 2 + C 2 H 4 A1(C 2 H 5 ) 3 + C 2 H^A1(C 2 H 5 ) 2 (C^H 9 ) A1(C 2 K $ ) 2 (G^K 9 ) HA1(C 2 H 5 ) 2 + C^Hq Heating the original reaction mixture for distillation might allow ethylene to be evolved in the known heat effect. The ethylene could then react with the aluminum-carbon bond in a growth reaction to form a variety of long chain substituents on the aluminum atom. This product could then break down to yield olefins and the compound with two ethyl groups on the aluminum atom. The fact that the aluminum atom contains only two ethyl groups, coupled with the molecular weight determinations which show the compound to be monomeric indicate that the product might be an odd electron molecule. The magnetic moment of a sample of this compound was measured on the Gouy balance and it was found that it is diamagnetic. The electron spin resonance spectrum confirmed this fact. Therefore, there are no unpaired electrons. This leads us

PAGE 91

82 to postulate the presence of an unseen hydrogen atom. A careful check of the n.m.r. and the infrared spectrum does not; reveal a single hydrogen fcom such as an A1H, an NH, or a PH group. A single A1H peak would not readily he seen in the n.m.r. spectrum because the spin of the aluminum nucleus is 5/2 and thus the Al-H peak would he a multiplet resulting from coupling with the aluminum nucleus and it would be broadened "oj the quadrupole moments of the uminum and the nitrogen. The single NH peak is often zoo broad to be seen for reasons £ _milar to those given for the A1H peak. A PH peak would probably be observed in the n.m.r. spectrum because it is split by about 200-300 cycles per second giving two peaks, and it is improbable that both peaks would be hidden. This information explains how a hydrogen atom could be bonded to aluminum or to nitrogen and not be observed in the n.m.r. spectrum. This leads us to postulate the presence of a single hydrogen atom in the molecule, probably bonded to the nitrogen or the aluminum atom giving the following formula for the compound: (C 2 E-) 2 N?(C 6 H^)2Ai(CpH 5 ) 2 H. If the hydrogen atom is attached to the nitrogen atom the molecule would be a zwitter ion because the nitrogen and the phosphorus would each be charged. All of this is of course speculation and indicates the need for additional work.

PAGE 92

b^ J. -~> ^ J.1U< «. ' 01 zae lors C. " , r. v -' • ' L ir. our . tor . • ^ ^ ...J .... . ... * . . . . . .luy i niolecu] t II of

PAGE 93

84indicates that the free pair of electrons on the nitrogen atom may be at least partially donated into the phosphorus d-orbitals. Under these circumstances, the phosphorus atoms would have a greater electron density and would be stronger basic centers than the nitrogen atoms. The proton n.m.r. spectrum of the bis(diphenylphosphino)methylaminetriethylaluminum adduct shows all the phenyl groups to be equivalent indicating that the phosphorus atoms have the same environment. The phosphorus n.m.r. spectrum supports this point of view since it shows only one kind of phosphorus atom. The combination of all the evidence again indicates pentacoordinate character for the aluminum atom because: First, chloramine reacts with bis(diphenylphosphino)methylamine to produce a compound, shown below, in which both phosphorus atoms have been attacked by chloramine, but the nitrogen atom remains tricoordinate. CH.N^ ° p 2 3 X P(C 6 H-) 2 NH 2 Second, the proton and phosphorus n.m.r. spectra show both phosphorus atoms to be equivalent. Third, the infrared spectrum does not show a peak at 1120 cm. which is associated with a normal tetracoordinate phosphorus containing a ?-phenyl bond. CI

PAGE 94

85 rherefore, considering these points we may again conclude that the phosphorus atoms are symmetrically located with respect to the aluminum atom. rhis must be considered as proof of the pentacoordinate character of the aluminum atom. The reaction of triethylaiuminum with bis(diphenylphosphino) ethyl amine is very similar to the reaction with bis(diphenylphosphino)methylamine. The main difference is the isolation of the reaction product. The molecular addition compound formed with bis(diphenylphosphino)ethylamine tends to hold onto the toluene solvent tenaciously. The difficulties in removing the last traces of toluene are responsible for the low yield as compared to the yield of the bis(diphenylphosphino)methylamine-triethylaluminum compound. The evidence for the pentacoordinate character of the aluminum atom in this compound is similar to that for the previous compound. The molecular addition compound was not stable at room temperature in the case of triethylaiuminum reacting with bis (diphenylphosphino) amine. In this case the nitrogen atom of the free base is bonded to a hydrogen atom and upon allowing the reaction mixture to warm to room temperature ethane gas is evolved. Molecular weight measurements on the resulting compound indicate that it exists as a dimeric species. An interesting conjecture concerning the structure

PAGE 95

ss of this dimer is to again consider the aluminum atom to be pent aco ordinate, bonding to two phosphorus atoms from another monomeric species to form the dimer. (C 6 H 5 ) 2^\ H _ A1 ^°2 H 5 y d K o p2 A model of this compound shows that the large size of the phosphorus atoms tends to cover or hide the nitrogen atom. For this reason steric interactions would probably prohibit the formation of a four-membered ring between the nitrogen and aluminum atoms. The infrared spectrum of this compound does not show the normal tetracoordinate phosphorus peak, so there is a good possibility that the aluminum atom is indeed oentacoordinate in this comoound.

PAGE 96

summary Chemical evidence, nuclear magnetic resonance spectral data, and infrared spectral data confirm the fact that the reaction of triethyl aluminum with several binuclear lewis bases, which contain tv:o diphenylphosphorus moieties, results in the formation of 1:1 adducts in which the aluminum atoms are pentacoordinate. Three compounds of this nature are described: tetraphenylbiphosphine-trie thyl ethyl aluminum, {0 '£.,-) ^^-^Oo' AlCCpE,-)^; bis(diphenylphosphino ) methyl amine-trie thyl aluminum , CH 5 N[P(C 6 n ! -)2^* A1 ( G ? H 5)-; and bis (diphenylphosphino)e thyl amine-trie thyl aluminum, CpH^NTPCC^KcOpjp-AlCCpH-),. Trie thyl aluminum reacts with tetramethylbiphosphine to form the 2:1 adduct, (CH 3 )pPP(CH 5 ) 2 '2Al(CpH 5 ) 3 , but not the 1:1 adduct. Triethyl aluminum, however, does react with dimethyl aminodimethylphosphine to form the 1:1 adduct, (CH,) NP(CH,) 2 -Al(C2H 1 -)2. An attempt to synthesize the 2:1 adduct yielded a small amount of material with the approximate composition of the desired material. The reaction of triethyl aluminum with diethylaminodiphenylphosphine yields a mixture of hydrocarbon compounds including ethylene and a compound containing two ethyl groups on nitrogen, two ethyl groups on aluminum and two 87

PAGE 97

88 phenyl groups on phosphorus. Since this compound is not dimeric nor paramagnetic it is postulated that there is a hydrogen atom present that cannot be seen in the n.m.r. or the infrared spectrum. The formula is postulated to be (C2Hc) 2 I ^( C 5 H :r)2 Al ( C 2 H 5' ) 2 H * Since the infrared spectrum still contains the peaks of the aminophosphine spectrum, there is no reason to believe the NP bond to be broken in the reaction. The reaction of triethyl aluminum with tertiarybutylaminodiphenylphosphine results in the formation of the 1:1 adduct, (CB.-,) 7 .ClTSP(C^E t -) 2 '^(0 o E^) 7 r, which is unstable above room temperature. Heating this compound results in the evolution of ethane to produce a monomeric compound having aluminum bonded to nitrogen, (CE 5 ) 3 CN[A1(C 2 K $ ) 2 ]P(C 6 H 5 ) 2 . The 1:1 adduct from the reaction between triethyl aluminum and isopropylaminodiphenylphosphine can not be isolated at room temperature. Ethane is given off and the aluminum atom forms a bond with the nitrogen atom producing the following trimeric compound, [(CH 5 ) 2 CHN{:U(G 2 H 5 ) 2 }?(C 6 H 5 ) 2 ] 3 . Ethane is also liberated in the reaction between bis(diphenylphosphino) amine and triethyl aluminum. The resulting product in this reaction is a dimeric material, [(C 2 H c -) 2 A1:'T{?(C-H [ -)2} 2 ^2' wilictl might possibly be another example of a compound containing pentacoordinate aluminum.

PAGE 98

PART II. A STUDY 0? THE CHLORAMINATION 0? SOME AMIN0PH03PHINE DERIVATIVES INTRODUCTION The reactions of chl or amine with phosphorus-containing compounds have been the subject of study in this laboratory for the last several years. A recent study concerned the reactions of chloramine with aminophosphines and showed that the effluent gases from the chloramine generator, that is, a mixture of chloramine and an excess of ammonia, react with aminophosphines to produce aminophosphonium chlorides rather than phosphinohydrazinium chlorides (19). All the previously reported chloraminations were, however, concerned with phenyl phosphino derivatives and none of them contained alkyl -phosphorus bonds. Furthermore, with the exception of 1 ,l-bis(diphenylphosphino)-2,2-dimethylhydrazine (56), none of the previously chloraminated nitrogen-phosphorus derivatives contained more than one phosphorus atom attached to a nitrogen atom. The present work was undertaken to determine if, as in the case of the previously studied aminophenylphosphines, chloramination of aminoalkylphosphines and of bis(diphenylphosphino) amines occurs on the phosphorus atom(s) rather .:.an the nitrogen atom. o* 89

PAGE 99

^ 90 Historical Background The preparation of chloramine in aqueous solution was developed by Rashig in 1907 (37) using the reaction of ammonia and hypochlorite ion: 001" + NH^ NH 2 C1 + OH" It was not until 1951 that the gas phase reaction was perfected allowing the convenient^preparation of anhydrous solutions of chloramine^ (38,39). This process utilizes the reaction between chlorine__an&_^an_excess of ammonia gas to produce chloramine in accord with the following equation: 2NH j(|) + 01 2(s) : ' H 2 C1 ( S ) + : "^ cl (s) Drajo (4-0) has reviewed the chemistry of chloramine providing a l3T~ief discussion of the preparations and the wide variety of reactions of chloramine. A more recent discussion (4-1.) provides a list of references concerning the reactions of chloramine with trisubstituted phosphines, and aminophosphines to produce phosphonium salts. A recent study in our laboratory has shown that a variety of di-, tri-, and tetraaminophosphonium chlorides results from the chloramination of different species of aminophosphines (19).

PAGE 100

91 r 2 np(c 6 e 5 ) 2 + :t?: 2 ci (R 2 IT) 2 ?(C 6 H 5 ) + NH 2 C1 1° 5

PAGE 101

92 According to this scheme the excess ammonia acts as a dehydrohalogenation agent. It was suggested that the insolubility of the final product prevents further dehydrohalogenation.

PAGE 102

[PSRIMENTAL s ~arial s During the course of this study precuations were taken to avoid contamination of solvents and other reagents by atmospheric oxygen and moisture. Solvents were dried by distillation from calcium hydride and storage over the same substance. Anhydrous amines were obtained from the Matheson Company, Incorporated, and were used as received. Diphenylchlorophosphine was provided by the Victor Chemical Works and was used without further purification. Tributylphosphine was obtained from Food Machinery and Chemical Corporation and was used as received. Dibutylchlorophosphine was prepared by the pyrolysis of tributyldichlorophosphorane (4-2) . nalyses Elemental analyses were done by Galbraith Microanalytical Laboratories. Melting points were obtained in wax-sealed capillary tubes in a Thomas-Hoover capillary melting point apparatus. ^rared spectra he infrared spectra were recorded on a Perkin-Elmer Model 137 spectrometer using sodium chloride optics. The 93

PAGE 103

9^ spectra of the solids v:ere obtained from Nujol mulls. A summary of the infrared data is found in Table 4. Tuclear magnetic resonance soectra The nuclear magnetic resonance spectra were obtained on a Varian high resolution spectrometer, Model V-4-300-2, equipped with field homogeneity control, magnet insulation, and field stabilizer. The shift values were obtained by sweeping through the field slowly and interchanging a reference sample and the sample being studied. In this x^ork acetaldehyde was used as the reference sample. The method produces the sample peaks and the acetaldehyde peaks on the same spectrum and from this the chemical shifts may be calculated in approximate y values. Phosphoric acid was used 31 as an external standard for measuring the P chemical shifts. The shift of the phenyl protons is measured from the highest peak. The H spectra were determined at 56. ^ 31 Mc ; the ? spectra, at 19.3 Mc. A summary of the n.m.r. spectral data is found in Table 5. Preparation of aminophosphines Some of the aminophosphines used in this work have been reported previously (19,29,35); however, the bis(diphenylphosphino) amines were synthesized in our laboratory prior to their description in the literature. The methods of synthesis described below are similar to the general

PAGE 104

95 methods reported in the literature (32,53,34,35). Dimethylaminodimethylphosphine was prepared by the method of Burg and Slota (27). The volumes of the gaseous amines used in this work were measured with a gas rotameter which had been calibrated with nitrogen. '"IsrninodibutylTshos nhi" (c^h 9 ) 2 pci + 2c 2 h 5 ::h 2 c 2 h 5 nh 2 -hc] + c 2 h 5 :;h?(c^h 9 ) 2 Twenty-nine liters (0.120 mole) of ethylamine was added slowly to a combination reaction and filter flask containing 50 ml of benzene. A short time after the addition of ethylamine was begun the dropwise addition of 9.20 grams (0.0509 mole) of dibutylchlorophosphine was initiated. The addition of the two reagents was carried out at such rates as to insure that the amine was always in excess. A white precipitate was formed immediately upon the addition of the phosphine. After the addition of ethylamine was complete the solution was stirred for an hour and then filtered under nitrogen. The solids were washed with four 15 ml portions of benzene and the filtrate was then evaporated under vacuum to yield the crude aminophosphine. The crude product was vacuum distilled to yield 5.38 grams of a colorless liquid boiling at 75° at 2.0mm. The yield based on the above equation is 35 per cent of theory.

PAGE 105

96 i infrared spectrum of ethyl aminodibutylphosphine is shown in ?i-~ure $2. Anal . Calcd. for C ? :-:-:;H?(C / ,H ) p : C, 63.^5; H, 12.73; N, 7.40; ?, 15.37. Pound: C, 63.27; H, 12.86; N, 7.24; ?, 15.20. The proton nuclear magnetic resonance spectrum of ethylaminodibutylphosphine is shown in Pigure 33. The spectrum is quite complex and all the peaks cannot be assigned with certainty. Peak A is a quartet assigned to the protons of the methylene group attached to nitrogen. Peak 3 is assigned to all other methylene protons. The rest of the spectrum arises from all the other methyl groups. The chemical shift values are recorded in Table 5, Bis ( diphenylphosphino ) ethyl amine 2(C 6 H-) 2 PC1 + 3C 2 H 5 NK 2 2C 2 H 5 NH 2 'HC1 + CgHJffCPCCgHc)^ To a solution of 59.5 grams (0.270 mole) of diphenylchlorophosphine in 200 ml of benzene was slowly added 9.9 liters (0.405 mole) of ethylamine. The addition of the ethylamine required two and one-half hours. However, after the first half hour the color of the solution was bright yellow. After an hour and a half the color of the solution began to diminish and when the addition of ethylamine was complete the solution was pale yellow. The solution was stirred for two hours after which time the solids were filtered and washed with two 15 ml portions of

PAGE 106

r\

PAGE 107

9S CM o g W (M o O Ph -P o CD Oh 03
PAGE 108

99 benzene. An attempt to isolate the desired product from the filtrate by the addition of hexane yielded a solid with a broad melting range. Hecrystallization of this solid from hot ethanol yielded 27.8 grams of bis(diphenylphosphino)ethylamine, 50 per cent of theory. The white crystalline product melted at 97-99° (Lit. 99°) (35). Figure 34 shows the infrared spectrum of bis(diphenylphosphino) ethyl amine. Anal . Calcd. for C 2 H-1T[?(C 6 H 5 ) 2 ] 2 : C, 75-53; H, 6.10; IT, 3.39; P, 14.99. Pound: C, 75-74-; H, 6.02; N, 3. .3; P, 14.75. The proton nuclear magnetic resonance spectrum of bis(diphenylphosphino)ethylamine, Figure 35 » has three peaks labeled A, B, and C. The peak A furthest down field, is attributed to the phenyl protons; the apparent quartet peak B, is attributed to the protons of the methylene group attached to nitrogen, and the triplet peak C, arises from the methyl protons. The large number of phenyl protons makes it impossible to examine the fine structure in peak A at the same time we examine peaks B and C. Bis(diphenylphosphino) methyl amine 2(C 5 Hc) 2 PCl + 3CH,NH 2 2CH 5 NH 2 'HC1 + CH^NCPCCgH^)^ By the method described above 4-4.0 grams (0.200 mole) of diphenylchlorophosphine was added to a solution of 5.64 liters (0.230 mole) of methylamine in 100 ml of benzene.

PAGE 109

l!o -i CO S-fe&feEfehniEE "" r~tr ~ .;.:,, .i~ -i~>-4— 100 C\J i — i oj •—\ LA w o cC I I !Zi w CM O O d ' -P o (D P< CO cu «H faO •H

PAGE 110

101 i — i Lf\ w o r—i Lf\ CM o o p o 0) Oh w Q) O d d o CO
PAGE 111

102 crude bis(diphenylphosphino)methylamine was obtained as a crystalline solid by evaporating the benzene solution under vacuum. Recrystallization from benzene-hexane yielded 17.0 grams, 55 per cent yield based on the above equation, of a white crystalline solid melting at 117-119° (Lit. 112115°) (35). The infrared spectrum of bis(diphenylphosphino)methylamine is found in Figure 36. Anal . Calcd. for CH,N[P(0 £ -H [ -) o ] o : C, 75.18; H, 5.80; i\ T , 3. 51; P, 15.51. Found: C, 74. 49; H, 5.99; N, 3.75; P, 15.45. The proton nuclear magnetic resonance spectrum of bis (diphenylphosphino)methyl amine , Figure 37, is quite simple showing a peak, A, for the phenyl protons and a triplet peak, B, for the methyl protons. Table 5 gives the chemical shift values. Bis (di phenyl phosphino) amine 2(C 6 H 5 ) 2 PC1 + 3NH 3 2:TH^C1 + HN[P(C 6 H 5 ) 2 ;! 2 3y the method described above, 11.9 grams (0.0540 mole) of diphenylchlorophosphine was combined with 1.98 liters (0.0810 mole) of ammonia in a reaction flask containing 75 ml of benzene. The color of the solution changed from colorless to bright yellow shortly after the reaction began. At the completion of the addition of reagents the solution was pale yellow and quite thick with

PAGE 112

103 OJ r1 OJ lA a o ^^ PM i — i 53 K\ W O O a -p o 0) Oa (0
PAGE 113

104 c\j i — i CM lA w O CM I I w o O fH +3 o (1) ft CO CD o d. o CO CD Fh o •H CD d to CCS CD O d m •H P>4

PAGE 114

o. s stirred for two hours after :olor '. the suspension A.fter L ; for 35 hours the soluf il b ere d . .'our >f benzene. The fiiora"; ,-, then evaporated Lting L bwice recry ;ure to yield 5-97 -' s of a v;l . : 'stalline solid melting at 14-5-146°, 58 per cent infrared spectrum of ;hiac' olote that the N3 ': a"j 3250 c ." . h, 3.64; P, 16. C . Hind: C, . ; H, . ; N, 3.62; p, 16. ;. stic r of bom m. I aomenon is not unusu il be'ect of elements with reac .on of lium chlorides roup and beg positivel ;ed.

PAGE 115

106 CM r— i OJ LA w O \s I I « o -P O
PAGE 116

107 h 2 ::?2 2 + :th 2 ci [(h 2 ::)(h 2 :0?^]ci The aminophosphonium chlorides are prepared by passing the effluent gases from the chloramine generator; chl or amine , excess ammonia ana nitrogen, through a solution of the aminophosphine to be chloraminated. Figure 39 shows a diagram of the chioramine generator used in this work. The rotametersa>e used to measure the volume of gaf^es^Th order to provide the following approximate quantities: ammonia, 1.2 moles per hour; nitrogen, 0.3 mole per hour; chlorine, 0.1 mole per hour. 'These concentrations provide a generation rate of chloramine of approximately 0.1 mole per hour according to the following equation: 2rri 3(g) + C1 2(S) :ra 2 C1 (g) + m 4 C1 ( S ) Aminodimethylaminodimethvlnhosphonium chloride (CE 5 ) 2 NP(CH 3 ) 2 + NH 2 C1 C(H 2 N) C(CH 3 ) 2 N} ?(CK 5 ) 2 ]C1 A solution of 1.62 grams (0.0154mole) of dimethylaminodimethylphosphine in 30 ml of benzene was chloraminated for 11 minutes. A white precipitate formed immediately and the solution became warm. The reaction mixture was allowed to stand overnight. The solids were then removed by _tration and extracted with chloroform to dissolve the phosphonium salt. The extract was uhen treated with hexane to precipitate 1.4-7 grams (61 per cent of theoretical) of a white crystalline solid melting at 190-193° •

PAGE 117

103 T3 o o' u o •p m hO CD U O o
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109 tie infrared, spectrum of aminodimethylaminodimetliylphosphonium chloride is found in Figure 40. Anal. Calcd. for C(H 2 N) {CCH 5 ) 2 h}p(CH 5 ) 2 3C1: C, 30.67; H, 9.01; IT, 17.39; ?, 19.78; CI, 22.64. Found: C, 30.66; H, 9.20; N, 18.06; ?, 19.89; CI, 22.27. The proton nuclear magnetic resonance spectrum of aminodimethylaminodimethylphosphonium chloride, Figure 41, shows the protons attached to nitrogen as a singlet peak A, the methyl groups attached to nitrogen as a doublet peak 3, and the methyl groups attached to phosphorus as a doublet peak C. This spectrum should be compared with the spectrum of dimethylaminodimethylphosphine, Figure 42. One of the main differences between these txvo spectra, other than the NH peak, is the fact that the coupling constants for the splitting of the protons from the methyl groups change from the aminophosphine to the phosphonium chloride, that is, the coupling constants for the dimethylaminodimethylphosphine are 10.1 and 5.7 cycles per second for the IT-CEU and the P-CEU protons, respectively, whereas, the coupling constants for the N-CH-, and P-CH-, orotons in aminodimethyl3 ' aminodimethyl phosphonium chloride are 11.1 and 14.5 cycles per second, respectively. Another difference between these spectra is the fact that the protons of the methyl groups on phosphorus are shifted down field in the chloramination product as compared with the starting material. This can also be considered as additional evidence of chloramination on the phosphorus atom.

PAGE 119

110 o i— i OJ w o I fU OJ w o OJ o a Ph -p o 0) w •d o rt H I I • o bO •H

PAGE 120

o I — I OJ !<\ w o CM 111 CO W o C\J !25 O s fH P o W CD O d cd d o CO o H .n CD d bO a rf CD rH o d HI rH faD •a

PAGE 121

112 J pq CM o OJ W o cm o -p o CD Oh W CD O Ctf d o CO o o •rH -P CD to e CD tH O Szs « OJ ho •H

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115 The basic hydrolysis of aminodimethylaminodimethylphosphonium chloride was found to occur according to the following equation: [(h 2 :0{(ch 3 ) 2 :;}?(ch 5 ) 2 ] + + e 2 o + oh" (CH,) 2 P(0)0H + NH, + (CH $ ) P ITH This experiment was performed on the vacuum line, the evolved gases were purified, identified by their vapor pressures, and their volumes were measured. There was no indication of the presence of any dimethylhydrazine which would have been present if the chloramination had occurred on the nitrogen atom. 'o' Aminoethylaminodibutylohosphonium chloride C 2 H 5 NHP(C Zj .H g ) 2 + M 2 C1 [(E 2 ^T)(C 2 H 5 2s T H)?(C^H 9 ) 2 ]Cl A solution of 1.10 grams (0.00581 mole) of ethyl aminodibutylphosphine in 50 ml of benzene was chloraminated for six minutes. A white precipitate formed and the solution became warm. The reaction mixture was allowed to stand for four hours. The solution was then filtered under nitrogen and the solids were washed with 15 ml of benzene. After the washing only a trace of solid remained and it is assumed that the solid is KH^Cl (from the decomposition of some of the chloramine). The filtrate was then evaporated under vacuum and the crude solids were recrystallized from a benzene-hexane solution to yield 1.18

PAGE 123

114 ..; of a white crystalline solid melting at 103-104° , per cent yield of theory. Figure 43 shows the infrared spectrum of aminoethylaminodibutylphosphonium chloride. Anal . Calcd. for [(H p :;) (C : ,E-:\H)P(C^H Q ) 2 ]C1 : C, 49.38; H, 10.89; N, 11.64; ?, 12.87; CI, 14.73. Found: C, 49.71; H, 11.02; N, 11.49; P, 12.87; CI, 14.41. Tne rather complex proton nuclear magnetic resonance spectrum of amino ethylaminodibutyiphosphonium chloride is shown in Figure 44. The A peak, which is assigned to the NHp group, is split in an unusual pattern for this group. The 3 peak is assigned to the protons of the methylene group bonded to nitrogen and the C peak is assigned to the protons of the methylene groups bonded to phosphorus. The rest of the spectrum is attributed to the remainder of the methylene and methyl protons. The chloramination product of bisCdiphenylnhosohino) ethyl C 2 E^T[P(C 6 HV ) 2 ] 2 + NH 5 + NH 2 C1 ii p C 2 HcN. X (C 5 H 5 ) 2 NH 2 CI + NH^Cl

PAGE 124

115 o i— i CM w O P4 LA w OJ O (\J o 3 f-i -p o CD P) W d CD H (0 H «H bO •H

PAGE 125

116 o i — i CM w — 1LA m CM o CM £ o a D fH -P O ft to o a o CO Sh o •H -P d cd S H O « ddfeO H Pn

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117 A solution of 2.57 grams (0.00574 mole) of bis(diphenylphosphino)ethylamine in 50 ml of benzene was chloraminated for 15 minutes. The reaction mixture was allowed to stand for three hours. The solution was then filtered under nitrogen and the solids washed with two 25 ml portions of benzene. The filtrate was evaporated under vacuum and the crude solids were recrystallized from a benzene-hexane solution to yield 1.75 grams of a white crystalline solid melting at 17&° with decomposition, 64per cent of theory. Figure 45 shows the infrared spectrum of this compound. NH ii / P( C 6 H 5^2 , 2V Lnal. Calcd. for C^Hr-N , (C 5 H 5 ) 2 NH, CI: C, 65.06; H, 5.8S; N, S.75; ?, 12.91; CI, 7.59. Found: C, 65.05; H, 6.02; N, 3.92; ?, 12.95; CI, 7.60. The proton nuclear magnetic resonance spectrum is found in Figure 4-6. Peaks A and A 1 are attributed to the two different phenyl groups, peak B the proton of the NH group, peak C the protons of the NHo group, peak D the protons of the methylene group, and the triplet peak E, the protons of the methyl group. It is interesting to note it the proton of the imino group is readily seen though quite broad.

PAGE 127

o o 00 -.1.... 118 CO •/f"^" J, ri-:tr:-:.i-rrr;:::.:L:;:i:;:.XJT:r;:: A ;-.-.•. ;\ --i z r> A±xts**±j.iLir^ixti;

PAGE 128

!~i ^0 4•H

PAGE 129

120 .c'r.l or ":-.• ir.?.~i en. ^roluct of bisCdiohenylrho.:'hino)metliyl amine .?(C 5 H 5 ) 2 CH^xn 3 \ P(CcHc)p I o 5 £ M 2 CI + NH^Cl A solution of 1.94 grams (0.00486 mole) of bis(diphenylphosphino)methyl amine in 30 ml of benzene was chloraminated for 12 minutes. The solution became warm during the chioramination. The reaction mixture was allowed to stand for 36 hours after which time the solution s filtered under nitrogen and the solids were washed with 10 ml of benzene. The filtrate was evaporated under reduced pressure to give a crude solid. This material was recrystallized from benzene to yield 1.31 grams of a white crystalline solid which melted at 166-163°, 58 per cent of theory. The infrared spectrum of this product is found in Figure 47. Anal. Calcd. for P(C 6 H 5 ) 2 ch 3 :t N P(C 6 H 5 ) 2 I CI: C, 64.44; 5.65; X, 9.02; P, 13.30; CI, 7.61. Found: C, 64.34; H, 5.57; N, 8.35; ?, 13.25, CI , 7.72.

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122 The proton nuclear magnetic resonance spectrum, Figure 4-8, is an excellent spectrum. The A and A' peaks are attributed to the phenyl groups, the B peak is the proton of the imino group which is tripled by 4.6 cycles per second, the C peak is the protons of the NH^ group, the D peak arises from the protons of the NCEU group coupling with the phosphorus atoms to give two peaks which are doubled by 5.0 and 14-. 4cycles per second, respectively. The chloramination product of bisCdit)henylnhosphino)amine HNCP(C 6 H 5 ) 2 ] 2 + HH, + NH 2 C1 -* NIL ^P(C 6 K 5 ) 2 >P(C 6 H 5 ) 2 NHo CI + NH^Cl A solution of 2.20 grams (0.00572 mole) of bis(diphenylphosphino) amine in 50 ml of dry benzene was chloraminated for 10 minutes. The reaction mixture was allowed to stand for 24hours and was then filtered under nitrogen. The solids were washed with three 50 ml portions of benzene and then extracted with four 50 ml portions of hot chloroform. The chloroform extraction separated the soluble phosphonium salt from the ammonium chloride. The phosphonium salt slowly crystallized from the chloroform as the known chloroform adduct, [(C 6 H 5 ) 2 P(NH 2 )NP(2m 2 )(C 6 H 5 ) 2 3Cl'HCC^ in 55 per cent yield.

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124 The infrared spectrum of the chloroform adduct is found in Figure 49. The chloroform adduct loses chloroform when heated under vacuum for two hours at 75°. The infrared spectrum of this product, Figure 50, is identical with the infrared spectrum of Ahuja's intermediate (4$). Anal. Calcd. for [(C 6 H 5 ) 2 P(NH 2 )NP(NH 2 ) (C^H^jCl-HCClj C $2.56; H, 4.41; II, 7.5&; P, 10.85. Found: C, 52.59; H, 4.59; N, 7.43; p, 11.21. Anal . Calcd. for C(C 6 H 5 ) 2 P(HH 2 )MP(HH 2 )CC 6 H 5 ) 2 3C1: N, 9.29. Found: N, 9.30. The proton nuclear magnetic resonance spectrum of this product, Figure 51 j shows a single peak, peak B, for the NHp groups. Note that there is no evidence for an imino KH group. The phenyl peak, A and A' , is so well resolved that, at first glance, it appears to be two peaks.

PAGE 134

rTT _ o o CO 125 ro\ O O o i — i OJ lA w O ^^ /"-> OJ OJ p-l OJ O O -P O
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126 o i — i OJ w O f— I ^ OJ w OJ LA W o o -P O o CO »d o Fi CT5 Fh d H I I * o LA h0 •H Pn

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o I — 1 O 127 OJ CM OJ a, w O o a fn -P O
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TABLE 4 INFRARED ABSORPTION IN CM (PART II)* 128 -1 3030(vs), 2960(vs), 2900(sh,vs), (CH,) P NP(CH,)p 2S40(vs), 1470(sh,s), 1450(s), J ° 1^-30(3), 1420(sh,n), 1290(s), neat 1190(vs), 1140(m), 1100(vw), 1060(s), 971 (vs), 93&(vs), 889(vs), 84-5(s), 811(m), 692(s). 3250(sh.vs), 3170(sh,vs), 29^0(vs), 2650(m), 2170(vw), C(H P N)-L(CH,)pN.rP(CH,) 9 ]Cl 1630(vw), 1570(m), 1460(vs), * ° * ° * 1420(s), 1380(m), 1310(vs), nujol 12?0(s), 1180(s), 1080(s), 987(b,vs), 951(s), 899(m), 856(s), 793(m), 752(a). 3450(sh,w), 3390(w), 29^0(vs), CpHc-NHPCC.Hq)^ 2900(sh,s), 1460(s), l^OO(m) , d > ^ d 1370(s), 13^0(w), 1290(w), neat 1260(w) , 1180(b,w), 1120(vs), 1090(sh,m), 1060(s), 1030(b, sh,w) , 1000(w), 9&&(w), 9350), 897(m), 810(b,sh,w), 781(sh,m), 725(b,m). 3190(s), 3120(sh,s), 29^0(vs), 2760(sh,w), 1560(w), 1460(vs), [(HpN)-C(C p H,)HN}P(C,H Q )p]Cl 1380(s), 1310(vw) , 1270(vw) , 25 ^ 2 1230(w), 1190(vw), 1130(s), nujol 1100(m), 1080(sh,m), 1060(w) , 1020(b,sh,w), 1000(sh,m), 988(s), 957(m), 901(b,w), 846(b,w), 802(w), 781(b,sh,w), 720(b,m). 3110(sh,m), 2960(vs), 2900(sh,vs), 1970(vw), 1890(vw), 1820(vw), CpH c .NCP(C fi H c .)p]p 1590(w), 1460(s), 1430(s), 5 b -> d d 1370(s), 1300(w), 1180(vw), nujol 1150(m), 1090(s), 1060(s), 1030(111), 998(w), 966(w), 924(m), 879(s), 85^(w), 766(m), 7^9(s), 7^2(s), 738(sh,s), 695(b,s). s, Strong; m, medium; w, weak; sh, shoulder; d, doublet; b, broad.

PAGE 138

129 Table HCont'd NH / ?(C 5 H 5 ) 2 C 2 H 5 K \ X P(C 6 K 5 ) 2 ITH 2 nujol CH 3 N[P(C 6 H $ ) 2 ] 2 nujol CI NH /P(C 6 H 5 ) 2 CH 2 N V x P(C c .H c; ) I o 5'2 NH 2 HN[P(C 6 H 5 ) 2 ] 2 nujol CI [(C 6 H 5 ) 2 P(NH 3 )NP(NH 2 ) ( nujol (C 6 H 5 ) 2 ]C1«KCC1 3 3210(sh,s), 29^0(vs), 19S0(vw) , 1890(w;), 1820(vw), 1590(m), 1560(sh,w), 1^70(sh,m), 14-60 (vs), 1^30(vs), 1370(s), 1280(b,sh,s), 1250(sh,s), 1220(vs), 1180(sh,s), 1180(sh,n), 1120(vs), 1090(m), 1070(n), 1030(w), 998 (m), 969(s), 937(a), S61(w), S50(w) , 79S(w), 765(m), 7^6(s), 727(s), 719(vs), 89C(b,vs). 3110(sh,vs), 2990(vs), 1960(vw), 1890(vw), 1820(w), 1650(vw), 1580(n), 1470(vs), 1^30(vs), 1420(sh,m), 1380(s), 1^10(m), 1270(m), 1170(m), 1160(sh,m), 1090(vs), 1070(vs), 1020(m), 998(m), 966(vw), 917(d,w), 831(vs), 7^3(vs), 695(vs). 3180(sh,s), 3100(sh,vs), 2970(vs), 1910(w), 1820(vw), 1680(vw), 1580(d,m), 1480(sh,m), W0(s), 14p0(vs), 14-20(sh,m), 1380(n), 1270(b,vs), 1180(d,m), 1160(sh,m), 1120(vs), 1090(s), 1030(m), 1000(s), 9^7(s), 907(w), 862(m), 84-9(sh,w), 781(w), 756(s), 72^(vs), 691(b,vs). 3250(m), 3080(sh,m), 2960(vs), 2880(sh,s), 1960(vw), 1890(vw), 1810(vw), 1480(sh,s), 1460(s), 1^30(s), 1380(s), 1300(vw), 1270(vw), 1250(m), 1160(b,w;), 1100(s), 1070(sh,w), 1020(m), 997(w), 916(sh,m), 905(sb,s), S97(vs), 79^(si), 7^9(s), 736(vs), 692(b,vs). 3250(sh,m), 3130(sh,s), 2990(vs), 1590(v/), 1570(sh,w), 1^70(vs), 1440(sh,s), 13S0(s), 1280(d,vs), I250(sb,s), 1180(w), 1130(s), 1120(sh,s), 1030(w), 998(w), 952(b,m), 922(sh,w), 7^-7(b,vs), 724(vs), 690(vs).

PAGE 139

2 w u bu e • •H i-t Dos ;? o o u cu 4-1 CO as co 3S CJ m w •J H M O M H W Z o * 0) — I > V re B H O S-i a a
PAGE 140

05 .

PAGE 141

discussic:: a::d conclusions One of the principal purposes of this study was to determine if chloramination occurs on the phosphorus atom in aminophosphines containing al ley 1 -phosphorus bonds or whether hydrazinium chlorides would be produced. It has been shown that the chloramination of tertiarybutylaminodiphenylphosphine produces aminotertiarybutylaminodiphenylphosphonium chloride (19). One proof given for chloramination of the phosphorus rather than the nitrogen atom, in this case, is the hydrolytic data obtained from basic hydrolysis of a sample of this material. Basic hydrolysis gives ammonia, tertiarybutyl amine, and di phenyl phosphinic acid. If chloramination had occurred on the nitrogen atom tertiarybutylhydrazine would have been a product of the hydrolysis reaction. This work shows that aminophosphines containing alkyl -phosphorus bonds also react with chloramine to produce phosphonium chlorides rather than hydrazinium chlorides. Basic hydrolysis of the chloramination product of dimethyl aminodimethylphosphine yields ammonia, d imethyl amine , and dimethylphosphinic acid. If chloramination had taken place on the nitrogen atom a hydrazinium chloride would have been produced and basic hydrolysis would have yielded dimethylhydrazine. 132

PAGE 142

155 arther proof of chloramination en the phosphorus Dm is provided by the n.m.r. spectrum of the phosphonium salt produced ~ozr chloraminating dimeainodimethylphosphine. In this spectrum the protons of the methyl -oups on the phosphorus atom are shifted down field as compared with the starting material. This fact is sup51 ported by the ? nuclear magnetic resonance spectra of the chloramination products of the aminophosphines as compared to the starting materials. The phosphorus peak is shifted down field in each case giving further proof that chloramination occurs on the phosphorus atom rather than the nitrogen atom. The chloramination products of the bis(diphenylphosphino) amines which contain an imino nitrogen atom on one of the phosphorus atoms show only one very broad peak 51 in the y P n.m.r. This peak is shifted up field from the starring material. It is possible that the observed peak arises from the phosphorus a"i:om containing the imino nitrogen atom and the peak from the other phosphorus atom is too broad to be seen. The up field shift of the phosphorus peak is interesting in comparison with the down field shift mentioned above. An attempt to correlate this information with the literature points up the fact that "jhere is no information readily available concerning the chemical shift of a ohosohorus atom containing an imino

PAGE 143

134 nitrogen group. These n.m.r. data are compiled in Table 5. Two new phosphonium salts have been produced in this study which contain alkyl -phosphorus bonds through the reaction 02 chloramine with dimethylaminodimethylphosphine and with ethylaminodibutylphosphine. These compounds are aminodimethylaminodimethylphosphonium chloride, [(H p N)(CH,)2NP(C^Hq)2]Cl, and aminoethylaninodibutylphosphonium chloride, [(H^:O0 p H^:I?:?(G^Hq) 2 ]C1. The ethyl aminodibutylphosphine used as a starting material for the last compound is itself a new compound. The second principal purpose of this study was to determine how chloramine would react with a series of compounds which contain two phosphorus atoms attached to a single nitrogen atom. The compounds synthesized for this study are bis(diphenylphosphino)ethylamine, CpHcNCPCCgH,-^^' bis(diphenylphosphino)me"chylamine, CH-N [P(C f -H c -)p]p; nnd bis(diphenylphosphino)amine, HNCPCCgH,-)^]^' 3is(diphenylphosphino) ethyl amine and bis(diphenylphosphino)methylamine have recently been reported in the literature (35). Our studies show that the chloramination of these compounds might very well proceed in an analogous manner co that postulated for the chloramination of 1,1-bisdiphenylphosphino-2,2-dimethylhydrazine (36), that is

PAGE 144

135 EN[P(C 6 H 5 ) 2 ] 2 + NH 2 C1 HIT i 2 RN / P(C 6 H 5 ) 2 X P(C 6 H 5 ) 2 ci + nh 2 ril \ r H 2 /^C 6 H 5 ) 2 X P(C 6 H 5 ) 2 NH CI + NH^Cl NH i(c 6 H 5 ) 2 N + NH 2 C1 P(C 6 H 5 ) 2 SIT P(C 5 K 5 ) 2 / © > y 2 NEU CI It is thought that, since the effluent gases from the chloramine generator contain a large excess of ammonia, the ammonia acts as a dehydrohalogenation agent. Solubilities must also play an important role because if the initial chloramination product were completely insoluble in benzene the reaction would not be expected to proceed beyond this point. The final product must be relatively insoluble or we would predict that the excess of ammonia would again dehydrohalogenate the chloramination product. However, in the case of bis(diphenylphosphino)amine, HNCPCCgHjOoDpi "the resulting product is [(CgHc) 2 P(NH 2 )NP(NH 2 )(C 6 H ( -) 2 ]Cl which is a known compound (4-3). This is a tautomeric form of the compound expected

PAGE 145

136 from the reaction sequence postulated above. The hydrogen atom from the original amine has migrated yielding the above compound which can be represented by the following formula: NIL I N /P(C & H 5 ) 2 CI %>(C 6 H 5 ) 2 NH~ The proton nuclear magnetic resonance spectra clearly show the NH groups and the NH 2 groups in the compounds where there is an alkyl group attached to the original amine nitrogen. The n.m.r. spectrum of the compound formed by the chloramination of bis(diphenylphosphino) amine only contains one type of hydrogen attached to nitrogen. The ^ P spectrum of this compound has been previously reported (4-3) to show a single peak for the two phosphorus atoms which confirms the equivalence of the groups attached to phosphorus. The nuclear magnetic resonance data are summarized in Table 5. The infrared spectral data are summarized in Table L v. Some of the spectral bands noted can be readily assigned while others remain uncertain. In order to facilitate the correlation of the data in Table 4, see Table 2, which contains the common spectral bands that may be assigned with certainty (22).

PAGE 146

157 The phosphonitrilic compounds which have been studied show strong absorptions in the range 1 320-1150 cm. that have been assigned to the PN linkage stretch (4-4) . All the chloramination products of the bis(diphenylphospheno) amines contain bands in this area of the spectrum. However, when there is an N=P— NP— N group this band is broad. All the chloramination products which contain phosphorus phenyl bonds are noted to contain the peak at about 1120 cm." . This peak has been assigned to the tetracoordinate phosphorus atom containing ?-phenyl bonds (19). Aminoethylaminodibutylphosphonium chloride contains a strong peak at 1130 cm." but the starting material, ethylaminodibutylph'osphine, also contains a very strong peak at 1120 cm. . This peak is not present in dimethyl aminodimethylphosphine or its chloramination product.

PAGE 147

SUMMARY Trie infrared ana hydrolytic data for the various chloramination products reported herein confirra the fact t the chloramin .ion occurs on the phosphorus ate::: rather than the nitrogen atom. ?or example, hydrolysis of the chloramination product of dimethyl aminodimethylphosphine yields only dimethylphosphinic acid, ammonia, and dimethyl amine, with no trace of a hydrazine derivative. Further, the infrared spectra of the chloramination products i oh contain P-phenyl bonds all exhibit the strong peak at about 1120 cm." which has been assigned to a tetracoordinate phosphorus atom having a P-phenyl bond. Analytical n.m.r. and infrared data show clearly . it the chloramination of compounds of the type RN[P(C,-H,-)p]p result in the combination of the bisphosphinoamine with two moles of chloramine in accordance with the following equation: tip A reasonable rationalization of this result would involve Le assumption that the initial monochloramination product :?(C 6 H 5 )p] 2 + 2NE 2 C1 + NH^ RI CI + NH^Cl 13S

PAGE 148

139 undergoes dehydrohalogenation and ohus regains in solution and available for the second chloramination steo. RU[P(C 6 H 5 ) 2 ] 2 + NH 2 C1 ..RN I 2 / P < 6 H 5>2 P(C 6 H_) 2 CI \ — -j p P (C 6 H 5 ) 2 (C 6 E 5 ) 2 CI + 2NEL 3 it / P(C 6 H 5 ) 2 X P(C 5 H 5 ) 2 ::h / ?'(C 6 K 5 ) 2 RN + NH^Cl X ?(C 6 H 5 ) 2 /(C 6 E 5 ) 2 \ ?(c & :-: 5 ) 2 ci In the case of the compound HN[P(C 6 H,-) 2 ] 2 the chloramination product obtainable according to this reaction sequence, viz. , H I! P f P TT N /^^ 6 M 5 ; 2 HIT \ CI P(C 6 H 5 ) 2 ::h 2 is a tautomer of the known compound C(C 6 H 5 ) 2 P(NH 2 )NP(ITH 2 )(C 6 H I -) 2 ]C1 and would be expected to rearrange to yield that compound. Analytical, infrared, and n.m.r. data si :hat this is the case and orovide further

PAGE 149

140 evidence for the preference of the ciorarr.ine molecule for attack on the phosphorus rather than the nitrogen atom.

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u?:-:y P. Cl ;ens, V/ I'. S. 3rey Jr. . r, Inorg. Ches. , : 12 ). 3. 3. V/i ;, H. C-ro ' R, Ulson, Z. anorg. u. Dhem., 272, 221(1958). 4-. John K. Ruff , rederi wthorne, J. Am. 0". Soc, S3, 535(1961). 5. C W. : . :. Nordsian, and 2. ".:. Parry, I -» 2, 5. I. K: ad P. Di .-. , 3, 2401(1930). 7. Horber:; C. Brov/n, J. A:... . Soc, _ . > ) . S. 2. ... . H. 2T5th, Z. . 'forsch, 1 , . • G. a. It Angew. 5, 725(1963). 10. A. 3. I ... . :er, J. Inorg. itfucl. Ch _ ). 11. rylig, Z. . urfor: _.. 12. id ?. Krech, Z. anorg. u. all ; :... ; ). ;erson and M. Onvszchuk, Canad. J. .,39, L). ~" . Lelsen . . r, J. Chea. Soc , L5. W. Br >, K. H. liele, I E. K. Muller, Z. Chem. ,

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142 18. Neil R. Fetter, 3odo 3artocha, Frederick S. 3rinckman, Jr., and Donald V. Moore, Ganad. J. Chem. , 41, 1359 (1963). 17. Neil R. Fetter, Frederick 3. 3rinckiaan, Jr., and Donald W. Moore, Canad. J. Chem., 40, 2184(1962). 18. Selected Values of Properties of Hydrocarbons and Related Compounds, American Petroleum Institute Research Project 44, Table IK. 19. William A. Hart and Harry H. Sisler, Inorg. Chem., 3, 617(1964). 20. J. C. Sheldon and 3. V. Tyree, Jr., J. Am. Chem. 3oc, 81, 6177(1959). 21. K. L. Paciorek and R. Kratzer, Inorg. Chem., 3, 594 (1964). 22. L. J. Bellamy, The Infrared Soectra of Complex olecules . John Wiley and Sons, Inc. (1958) . 23. J. E. Mayhood and R. 3. Harvey, Canad. J. Chem., 33, 1552(1955). 24. R. A. Mclvor and C. 3. Hubley, Ganad. J. Chem., 37, 869(1959). 25. Anton 3. 3urg, J. Am. Chem. Soc, 83, 2226(1961). 26. Alfred C-. Garrett and Grant Urry, Inorg. Chem., 2, 400(1963). 27. Anton 3. 3urg and Peter J. Slota, Jr., J. Am. Chem. Soc. , 80, 1107(1958). 28. Robert R. Holmes and Raymond P. Wagner, J. Am. Chem. Soc, 84, 357(1962). 29. Anton 3. 3urg and Peter J. Slota, Jr., J. Am. Chem. Soc, 82, 2145(1960). 30. John D. Roberts, Nuclear Magnetic Resonance . McGrawHill Book Company, Inc. (19?9) . 31. H. Zeiss, O rganometallic Chemistry . Reinhold Publishing Corporation (I960).

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1-4-5 Harry H. Sisler and Nathan L. Smith. J. Org. Chem., 26, 511(1951). C-. Ewart, D. 3. Payne, A. L. Porte, and A. ?. Lane, J. Chem. Soc, 1952, 395^. ; . A. Michaelis and K. Luxembourg, 3er. , 8, 2205(1395). 55. 0. Swart, A. ?. Lane, J. McKechnie, and D. S. Payne, J. Chem. Soc, 1954, 154-3. 52. 33 Robert P. Nielsen, Joseoh 3. Vincent, and Harry H. Sisler, Inorg. Cher.., 2, 760(1963). 37. 3. Rashig, 3er. , 40, 4-536(1907). 38. R. Mattair and H. H. Sisler, J. Am. Chem. Soc., 73, 1619(1951). — 39. H. H. Sisler, 3. 1. Neth, R. 3. Drago, and D. Yaney, J. Am. Chem. Soc, 76, 3906(1954). 40. R. 3. Drago, J. Chen. Educ , 34, 54(1957). 41. W. A. Hart, S tudies of the Chloramination of Aminoph: Derivatives . Ph.D. Dissertation, University of 3iorio.a, August, 1963. 42. S. 3. 3razier, R. P. Nielsen, and H. H. Sisler, Inorg. m., 3, 292(1964). 45. Harry H. Sisler, H. 3. Ahuja, and Nathan L. Smith, jrg. Chem., 1, 84(1962). . L. W. Daasch, J. Am. Chem. Soc, 6, 3403(1954).

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BIOGRAPHICAL SKETCH Donald Faull Clemens, was born August 14, 1929, in Dover, Ohio. In June, 19^7, he was graduated from Lover ;h School. After graduation from high school he worked as a machinist for the Greer Steel Company in Dover until June, 1957. At this time he began his college education at Florida Southern College in Lakeland, Florida. ProJune, 1953, until June, 1961, he worked as a laboratory assistant in the Department of Chemistry at Florida Southern College. He received the degree of Bachelor of Science from Florida Southern College in June, 1961. Upon graduation be enrolled in the Graduate School of the University of Florida. He received the degree of Master of Science in April, 196$. He worked as a research fellow and as a teaching assistant while pursuing his graduate degrees. Mr. Clemens is married to the former Martha K. Lemmon and is the father of five children. He is a member of the : Lie lodge, the Methodist Church, and Who's Who Am Lg Students in American Universities and Colleges (I960-: 1). 144-

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.is dissertation was prepared under the direction of the chairman of the candidate's supervisory committee and has been approved by all members of that committee. It was submitted to the Lean of the College of Arts and Sciences and to the Graduate Council, and vras approved as partial fulfillment of the requirements for the c of Doctor of Philosophy. April 24, 1955 Dean, Co Dean, Graduate School Supervisory Committee LUA, 3 dsYlj/l^ --">


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