Group Title: study of the reactions of some nitrogen and phosphorus bases: (I) with triethylaluminum; (II) with chloramine
Title: 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
Physical Description: viii, 144 l. : illus. ; 28 cm.
Language: English
Creator: Clemens, Donald Faull, 1929-
Publication Date: 1965
Copyright Date: 1965
 Subjects
Subject: Triethylaluminum   ( lcsh )
Chloramine   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Thesis: Thesis - University of Florida.
Bibliography: Bibliography: l. 141-143.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
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Bibliographic ID: UF00097895
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000423997
oclc - 11062823
notis - ACH2402

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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.,









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-- -!----- 1--1 --
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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


Tu




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0













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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























I
n-r, ,- r-- rnr
Ir ~





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


-' ^ `"" :I"
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+ J + I I i 'i ... t 'i + :: i .... + -

I!i.i --; I I11
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...........
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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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S..... ...... .. .. ..... .. ..... ...........
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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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0 : : :i: : : ::j ::i:m:: ;


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0
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o
i o3


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0
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0
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, O

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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




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