• TABLE OF CONTENTS
HIDE
 Title Page
 Acknowledgement
 Table of Contents
 List of Tables
 List of Figures
 Introduction
 The synthesis of antimony-nitrogen...
 The synthesis of antimony-nitrogen...
 The preparation of various...
 General conclusions
 Bibliography
 Biographical sketch














Group Title: synthesis of antimony-nitrogen compounds by ammonolysis and chloramination reactions
Title: The synthesis of antimony-nitrogen compounds by ammonolysis and chloramination reactions
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Permanent Link: http://ufdc.ufl.edu/UF00098216/00001
 Material Information
Title: The synthesis of antimony-nitrogen compounds by ammonolysis and chloramination reactions
Physical Description: viii, 182 l. : illus. ; 28 cm.
Language: English
Creator: McKenney, Robert Lee, 1936-
Publisher: s.n.
Place of Publication: Gainesville
Publication Date: 1966
Copyright Date: 1966
 Subjects
Subject: Chloramine   ( lcsh )
Antimony   ( lcsh )
Nitrogen   ( lcsh )
Infrared spectra   ( lcsh )
Nuclear magnetic resonance   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Thesis: Thesis - University of Florida.
Bibliography: Bibliography: l. 179-181.
General Note: Manuscript copy.
General Note: Vita.
 Record Information
Bibliographic ID: UF00098216
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 - 000427111
oclc - 11084926
notis - ACH5853

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Table of Contents
    Title Page
        Page i
        Page i-a
    Acknowledgement
        Page ii
    Table of Contents
        Page iii
    List of Tables
        Page iv
    List of Figures
        Page v
        Page vi
        Page vii
        Page viii
    Introduction
        Page 1
        Page 2
        Page 3
        Page 4
    The synthesis of antimony-nitrogen compounds by chloramination with ammonia-free chloramine, and subsequent reactions of the products
        Page 5
        Page 6
        Page 7
        Page 8
        Page 9
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        Page 109
        Page 110
        Page 111
    The synthesis of antimony-nitrogen compunds by ammonolysis
        Page 112
        Page 113
        Page 114
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        Page 118
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        Page 140
        Page 141
        Page 142
    The preparation of various derivatives
        Page 143
        Page 144
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    General conclusions
        Page 167
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        Page 172
        Page 173
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        Page 178
    Bibliography
        Page 179
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    Biographical sketch
        Page 182
        Page 183
        Page 184
        Page 185
Full Text













THE SYNTHESIS OF ANTIMONY-NITROGEN
COMPOUNDS BY AMMONOLYSIS AND
CHLORAMINATION REACTIONS









By

ROBERT LEE McKENNEY, JR.


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
December, 1966












ACMLCWL EDGt'ENNTS


The author wishes to express his gratitude to his

research director, Professor Harry H. Sisler. Dr. Sisler,

although extremely busy with administrative responsibili-

ties, always found time to offer helpful suggestions and

advice concerning this author's research. It is also known,

that without Dr. Sisler's personal effort, this author

would never have had the opportunity to perform this work.

The author also gives his sincere thanks to the

other members of his committee for their interest shown in

the preparation of this dissertation.

A special note of thanks is extended to Dr. Surt

Utvary and Dr. Joseph M. Kanamueller for the many helpful

discussions that took place during'the course of this work.

Also, the author recognizes the friendly assistance

received from his former colleagues, Dr. Donald F. Clemens

and Dr. Stephen E. Frazier.

The author acknowledges the National Science Founda-

tion for their generous financial support of this work.

Finally, the author expresses his sincere grauit-ude

to his wife, Joy, and daughter, Kathy, for their many

sacrifices incurred during the performance of this work.












TABLE OF CONTENTS

Page

ACKNOLEDGMENTS . . . . . . . . . ii

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

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

CHAPTER

I. INTRODUCTION. . . . . . . . . 1

II. THE SYN'HSESIS OF ANTIiONY-NITROGEN COMPOUNDS
BY CELOL- NATION WITE A0MI-iONIA-FREE
CELORAM-INE, AND SUB3SE-UENT REACTIONS OF
THE PRODUCTS . . . . . . . 5

cExerimental . . . . . . . 5

Discussion . . . . . . . . 90

III. THE SYNTHESIS OF ANTIMO If-NITROGEN COMPOUTjDS
BY AMONOLYSIS . . . . . . .. 112

Experimental . . . . . . . 112

Discussion . . . . . ... 136

IV. THE PREPARATION OF VARIOUS DERIVATIVES OF
THE TYPE (CgH5) j Sbo. . . . . . 143

Experimental . . . . . . 143

Discussion . . . . . . . 160

V. GENERAL CONCLUSIONS . . .. . . .. 16

BIBLIOGRA-PHY. ...... . . . . . 179

BIOGRAPHICAL SKETCH . . . . . . . 182


iii












LIST OF TABLES


Table
-1
1. Infrared Spectral Data, Cm-1 . . . .

2. X-ray Powder Data for [(n-C 3E7)Sb(Cl)] 2O0.
-1
3. Infrared Spectral Data, C:1 . .

4. Infrared Spectral Data, Cm-1. . . . .

5. Nitrato Abscrption Frequencies in [R3Sb(ONTO2
Compounds (Cm ~) . . . . . . .

6. Sb-O-Sb and Sb-ZTH-Sb Infrared Frecuencies
(Cm- ) . . . . . . .

7. Proton Magnetic Resonance Data, . . .


Page

. 7

. 57

. 114

S 144


171


. 175

. 175










LIST OF FIGURES


Vacuum line . . . . . .


Page

. . 13


2. Distillation curve for ammonia-free
chloramine. . . . . . . .

3. Infrared spectrum of (CH3) SbBr2 . .

4. Proton magnetic resonance spectrum of
(CH ) Sb3r2 .. .
( 3Ci3) 2br . . . . . . .

5. Infrared spectrum of (CH)Sb . . .

6. Infrared spectrum of (n- H)3Sb. . .

7. Infrared spectrum of (C25Sb. . . .

8. Infrared spectrum of [(CH 3)Sb(C1)]2N. .

9. Proton magnetic resonance spectrum of
[(CH ) Sb C1)] 2NH . . . . .

10. Infrared spectrum of [(C25)3 Sb(Cl)]2 'T

11. Proton magnetic resonance spectrum of
[(C2H 5 ) Sb(C 1)] . . . . . .

12. Infrared spectrum of [(n-CH7)3SSb(Cl)] 2N

13. Proton magnetic resonance spectrum of
[(n-C E7)Sb(Cl)] 2N. . . .

14. Infrared spectrum of [(n-CH9Q)3Sb(Cl)]2IT'

15. Infrared spectrum of (r-CZ ,jSb. .

16. Proton magnetic resonance spectrum of
[(n-Cz 9)3Sb( ) . . . . .

17. Proton magnetic resonance spectrum of
(n-C 9) SS b . . . . . . . .

18. Infrared spectrum of [(C6H)3Sb(C1)]2FH


Figure

1.


. . 14

. . 17


S. . 18

S. 20

S. 21

. . 23

. 26


. .

. .



* .


* 4








Figure Page
19. Infrared spectrum of (C6H5) Sb . . .. 45
20. Infrared spectrum of (CH5)SbC12 . . .. 46
0 5 5 2.
21. Proton magnetic resonance spectrum of
C(C6H5 )Sb(Cl)]2- . . . . . . 47
22. Proton magnetic resonance spectrum of
(C6H5)%Sb. . . . . .. . 48
23. Infrared spectrum of [(CH) 3Sb(C1)]20. . . 51
24. Proton magnetic resonance spectrum of
C(CH3)3Sb(C1)]20 (CDC13) . . . . . 52
25. Proton magnetic resonance spectrum of
[(CH3)3Sb C1)]20 (H20) . . . . . . 53
26. Infrared spectrum of [(C2H5)3Sb(C1)]20 . . 55
27. Proton magnetic resonance spectrum of
[(C25)3Sb(C)2. . . . . . 56
28. Infrared spectrum of [(n-03H7)3Sb(Cl)O20 . 58
29. Proton magnetic resonance sDectrum of
[(n-C3H7)Sb(C1)]20. . . . . . . 59
30. Infrared spectrum of [(n-C4HE9)Sb(1C)]20 . 61
31. Infrared spectrum of C(C6H5)3Sb(C1)]20 . . 63
32. Proton magnetic resonance spectrum of
[(C6H5)3Sb(Cl)]20. . . . . . 64
33. Infrared spectrum of Sb20 . . . 66
54. Infrared spectrum of (CH )-SbCl ....... 68
35. Proton magnetic resonance spectrum of
(CH3) SbC12. . . . . . . . . 69
36. Infrared spectrum of [(CH )3Sb(ONO2)]20. . 70
37. Proton magnetic resonance spectrum of
[(C 3)3Sb O2)]2 . . . . . . . 72









Figure Page
38. Infrared spectrum of (CEH)Sb(ONO) . . 74
39. Proton magnetic resonance spectrum of
(CH3)3Sb(ON02)2. . . . . .. . 75
40. Infrared spectrum of [(C2H5)3Sb(ONO2)p20 .. 77
41. Infrared spectrum of (n-C9 3bC2 .. . . 79
42. Infrared spectrum of (n-C49)2SbCl . . . 80
43. Proton magnetic resonance spectrum of
(C6H5) SbC 2 . . . . . . . . 82
44. Infrared spectrum of (CH) ~SbO. . . . 85
45. Infrared spectrum of (C6H5)3SbOO.3H20 . . 86
46. Proton magnetic resonance spectrum of
(C6H5)3SbO. .3H20. . . . . . . . 88
47. Infrared spectrum of [(C6H5) Sb(ONO2)]20 . 89
48. Proton magnetic resonance spectrum of
[(C 5 )3Sb(ON2)]20. . . . . . . 91
49. Plot of C(ar T-S frequency versus 1/ . 100
50. Infrared spectrum of a mixture
[(C6H )3Sb=N=Sb(C6H5) ]Cl (88%) and
[(C6H5)3Sb(C1)]2TH (12%) . . . . 116
51. Infrared spectrum of a mixture
[(C6H5) Sb'N=Sb(C6 H5)]C1 (75%) and
[(C06H5)Sb(Cl)]25H (25%) . . . . .. 118
52. Infrared spectrum of
[(C6H)SbN=(C65)6H )3]C12K-0.8c 78. . . 121
53. Proton magnetic resonance spectrum of
[(C6H )SbN3=Sb(CH6H )]C12K-0.8C7H8. . . 122
54. Infrared spectrum of the crude product from
the ammonolysis of triphenyldichlorostibane.. 129


vii









Figure Page

55. Infrared spectrum of (C6H5)5Sb . . . . 131
56. Proton magnetic resonance spectrum of
(C6 5)5Sb. . . . . . . . . 133

57. Infrared spectrum of (CHS)3 SbC12 N(CH )3. 135
58. Proton magnetic resonance spectrum of
(C6H5) SbC1 2N(CH ) . . . . . . 137-
59. Infrared spectrum of (C6H5)SbOH . . . 148
60. Infrared spectrum of (C6H5)4SbBr . . . 149
61. Proton magnetic resonance spectrum of
(C H 5)4SbOH. . . . . . . . . 150
62. Proton magnetic resonance spectrum of
(C6H5)4Sb3r. . . . . . . . . 152
63. Infrared spectrum of [(C6H5)4Sb]20 . . .. 153
64. Infrared spectrum of (CH 5)4SbONO2 . . . 155
65. Proton magnetic resonance spectrum of
(C6H5)4SbON02. . . . ... . . .. 156
66. Infrared spectrum of [(C6H5)4Sb]3(C6Hs)4 . 158
67. Proton magnetic resonance spectrum of
[(C6H5)4Sb]B(C6H ) . . . . . . 159
68, Comparison of phenyl proton signals from
various antimony compounds with that from
benzene. . . . . . . . . . 177


viii












CHAP1.AR I

INTRODUCTION


Aqueous chzlorar.ine tras f..r..ls pxo~rc1 .. .. ....; ia.

1'0'7 (1) by mixinr clilutle solutions 0o ar..loj.-: a ,.. }7.o-

c1., oCri be .on.

H + 001-> MH2 0 + OH

lattai.-r nd isler.o (2) succeeded i. pro.?ar"' .. .C. oUs

,aseous chloc.m..""ine in 1951 by the C::. phareo r-ac.-.on. of:

ox)cra.; (:malolia wi.Oh chlo'ime.

2U....) .0. P. ]- ..:.A. .l i J ..2 : 1. .

The ch -or.in e oactOionT :*i h. L,'." bno-s O. biee

,i'' .1ubjoct orf a rcthcr otonsPivo iru.i atio -. :3



a.;o :.l-mon.oz roact;:. .ith 12.. ..1.l-,. "" "o,' 8 On o :....'*-
),.. L ,-
_. ,. for- of year








"Chlo Ji : .il: 'o :o; n ;" ": '-"t i l .'.' : .I n. --

- ,and 1', :l. i_ l-.o' v;:.m ic o 'c ii '. t1lo ': o V.i . : .".5' -. c





r.y(. "Tr '.] .;, )r' (.) ii'{;i"X"liK 4 "r-'b ,-t; 3 8_' .' C.o i ^ .'t *;:'*:
C_1 j L











chloramination of trialkyl- and triarylarsines gives good

yields of aminoarsonium chlorides.

R As + N2C1 [ R3AslH2]C1

However, rigorously anhydrous conditions must be maintained

to prevent hydrolysis of the products obtained.

Other work using solutions of ammonia-free chloramine

(6) has been reported. The ammonia-chloramine mixture from

the gas phase reaction was passed into a solvent, usually

ether, and then freed of ammonia and all traces of water by

slowly passing the solution through a column of anhydrous

copper sulfate. Vacuum-line technique was then used to

maintain rigorously anhydrous conditions throughout the

remainder of each experiment.

Since compounds of the first three members of group

V of the periodic table were being rather extensively

studied with respect to their reaction with chloramine, the

next logical step was a similar investigation of antimony

compounds. This, therefore, has been one of the major

purposes of this work.

In 1964, Wittig and Hellwinkel (7) carried out the

reaction of triphenylstibine with Chloramine-T and obtained

(C53 )Sb=T-SOC2C6H C whi-h is probably the first compound
isolated containing a direct Sb(V)-T linkage. Some early

(8) and also some more recent work (9) involving the

hydrolysis of various trialkyldihalostibanes gave evidence










for the formation of comp-ounds of the type -,Sb(Oh)jOCl.

Appel 'rand co-worke:rs (10) desc.ibe the forimiation of

[(C.H) 5- Sb .TK] (X = C, B:, and I) 1frou. the reaction of

tripbhenylatibine imine with a vari Loty of reagjents. EoL.,.ver,

other w'.-okers (11,12,13,14,) have sho.n. t hat partial hycro.ly

sis of tr:ial]yl-- and bria-ry1dicblorostibanos yi.els ..ho

anhydride-like compounds R Sb(01)]20, and no -the h.ydrox

chlorides. On the basis of all the above information, ij

rwas posbulaled. ;ha; chlorauin.e I;tould r-.act .iTh various

tertiary stibines to yield coup.ou.nds of the type

[? 3b(C01)] I, possibly goin;: throu h t'he interr-idiatb

- '3 b' (' 2) C 1..

:Another major p.rpo-;e of this .ork has b,:.en to

study the reactions of liquid a:n.onia and li uid a"".onia-

pot.ass .- n anie with b'ip ?.enyldic. lotrostibano and tot ra-

he2nylb..romostibaae in order to obtain some new and.

inUeresting ant.i-a oynitro;en copouinds. Sijce, t onset

of this work, Appel et al. (10), rc orted the fin.in.s of

a very e:xtonsive sLudy of the : r'eacio of (CHt5 .)-.5 b:'2 (X

Cl, Br, and I) wibh somc alkali tal ani.des in liquid

ammonia. The reaction conditions vwer such Chat both

haloSen atoms wer e re. vd '-ro- the n.ti:rony, pOoducin

triphej.nst ibine in.oin ad in one case th co:'Iensation

product of the irine, (06H 5) Sb =lT-Sb(CH) G T5 (CH5) .5
0 9 9 O 5'3










Finally, an objective of this work has been to carry

out a qualitative infrared and proton magnetic resonance

study on as many organoantimony compounds as possible in

order to: (1) make tentative assignments to new absorption

bands in the infrared spectra; (2) learn more about the

polarity of the antimony-halogen bonds; (5) make specific

nuclear magnetic resonance data available.












CHAPTER II


THE SYNTHESIS OF A2TTIMON-NITROGEN COMPOUNDS BY
CHLORAMINATION WITH A'EIHONA-FREE CHLOPRAMINE,
AND SUBSEQUENT REACTIONS OF THE PRODUCTS


Experimental


Materials

Tri-n-butyl- and triphenylstibine were purchased

from M and T Chemicals, Inc. The former was redistilled

and the fraction boiling at 129-130C. (11 =m) was used.

Triphenylstibine was recrystallized from petroleum ether

before use. The solid melted at 52-54oC. Reagent grade

solvents were dried over calcium hydride. Technical grade

solvents were distilled from calcium hydride, then stored

over it.

Analyses

Elementary analyses were performed by Schwarzkopf

Microanalytical Laboratory, Woodside, New York, Crobaugh

Laboratories, Charleston, West Virginia and Galbraith

Laboratories, Inc., Knoxville, Tennessee. Chloride analyses

were usually carried out in this laboratory by the Volhard

technique. Melting points were obtained using wax sealed

capillaries on a Thomas-Hoover capillary melting point

apparatus and are uncorrected.










Molecular weights were determined by the cryoscopic

method using benzene as a solvent. A conventional freezing

point apparatus was modified to provide a slight flow of

dry nitrogen in order to minimize solution contact with the

atmosphere. The lower than theory molecular weights

reported for the nitrogen-containing compounds are indica-

tive of partial hydrolysis which undoubtedly occurred during

the determination.

Infrared soectra

Infrared spectra were obtained on a Beckman Model

IR 10 infrared spectrophotometer using potassium bromide

arnd cesium iodide optics. Solid state spectra were obtained

using Nujol and Kel-F mulls. The spectra of all the tri-

alkylstibines were obtained using thin films. All water

and oxygen sensitive samples were prepared in a dry box and

were stored in a dessicator until being placed on the

instrument, which was constantly being purged with a slow

stream of nitrogen. The infrared spectral absorptions are

listed in Table 1.

Proton magnetic resonance soectra

The proton magnetic resonance spectra were obtained

with either a Varian high resolution nuclear magnetic

resonance spectrometer, Model V-4300-2, provided with field

homogeneity control, magnet insulator, and field stabilizer,

operating at 56.4 or 60 Mc or with a Varian nuclear magnetic











INFRARED


TABLE 1
SPECTRa DATA,
SIPCTRAL DATA, Cm


(C3) 3Sb
Neat
(C3 ) SbBr (15)
Nujol

(CHn) SbC1l
Nujol
(CH ) Sb(GO02)2
Kel-F, Nujol




C(CH 3)Sb(Cl)]2 -i
Nujol


[(CH5)5Sb(C1)] 2H
[(CH 3) 3Sb(Cl)]20
KBr Pellet, Nujol


[(CH3),Sb(ONO) 20
Kel-F, NTujol



(02H5)3Sb
(eaC
Neat


2990(m),2915(m),1390(w),810(m),
512(s)


5012(w) 2927(w),2410(vw),1772(vw),
1723(vw ,1403(vl),1387(w),1352(vw),
1210(nvw-),870(s),564(m)
1210(w),870(vsb),573(s),277(s)


3035(w) 2938(vw),2798(v-w),220(vw),
1915(v), 1805(vw,b),1755(vw7),
1665(v,b),1550-15C0(vs),1400(i),
1300-1270(s),1240(m),1228(m)
965(vs),862(vs),833(m),792(m.,
728(s),708(m),578(m),505(w,sh),
278(m)
3225(m),2420(vw) 2330(vw),2055(vw),
1800(~r3),1750(vw),1645(vw,b),
1408(m) 1238(vw,sh),1209(w),1098(vw),
1055(vw),861(vs),741(vs),580(s),
535(w)
3010(vw) ,2920(vw) ,2420(vw),1800(vw),
1749(vw) ,1405(m),1228(w),1217(vt),
860(s),771(s.,b),585(s),53-(m),
285(w,b),265(w)
3010(m),2730(vw),2440(vw,d),2010(vw,d),
1795(w,b) 1720(w,b),1480-15S0(vs),
1310-1275(vs),1258(w),1222(w),
1018(vs),860(s),815(vs,sh),78S(vs,b),
715(vs),578(s) ,530(m),260(V'w)
2960(vs),2920(vs),2880(s),2835(w),
2740(vw),1465(m) ,142S()) ,130(M),
1235(vw),1185(m),1025(m),965('w,b),
700(m),685(m,sh),655(w,sh),500(m)


__ __









Table 1 (cont'd)


[(C2E5) Sb(Cl) 2iNT
Nuj ol

(C2H5) 3Sb(C1)]20
Nujol

[(C2 5) Sb(ONO2)]20
Nujol

(n-C E7) Sb
Neat



[(n-C3E7)3Sb(C1)]) 2NH
Nujol


[(n-C3H7) 3Sb(Cl)] 0
KBr Pellet, Nujol



(n-C4H 9) Sb
Neat




(n-C4 9) 2SbCl
Neat


3162(m,b) 1670(vw,b),1284(vw),
1212(m sh ,1193(s),1026(s),972(s),
758(vs),704(vs),558(m,sh),528(m),
497(w)
2760(vw),2166(vwi) ,1404(m),1200(s),
1063(w,sh),1025(m ,971(im),768(s,b),
713 s,b),647(m sh),545(m),498(vwn),
300(w,b),265(w)
2285(v,),1715(v~.),1480-1420(vs),
1285(vs),1220(w,sh),1208(m),1095(w)
1025(s sh),1013(vs) 980(m),815(s,sh3,
792(vs),702(vs),546m ),498(m)
2960(vs),2936(vs),2905(s),2870(s),
2820(w,sh),1450(m,sh),1455(m),
1415(vw),l157(w),1532(w),1275(w)
110(vw),1170(w sh),1155(w),O1068(w),
1020(vw) 995(vw),800(vw)i,720(vw,b),
680(vw,b ,655(w,sh),585(w),500(w)
3142(m),1657(vw,b) ,1417(w),1337(-w),
1242(vw),1202(vw) ,1174(m),116(w, sh),
1076(s),1012(s),815(w),752(vs),
692(s) 665(-w sh),613(w),595(vw),
516(vw ,422(wv
2960(m),2930(m),2870(n),1455(m),
1413(w),1373(:w),1335(w),1278(w),
1167(s),1075(s),1017(vw ,sh) 1008(s),
802 (v,sh) 754-734(s,I),696 s),
628(w),607(w) 522(w),395(w),300(m),
285(m,sh),260(n)
2960(vs),2930(vs),2880(s),2860(s),
2753(vw),1460 s),1420(w),1578(2),
1360(vw),1351 w),1294(w),1250(w),
1178(w) 1148(w),1080(w).1050(vw),
1022(vw),1005(w),961(w ),876(w,b),
770(vw),745(vw),686(w,b),590(w),
500(w)
2965(vs),2950(vs),2880(s),2870(s),
2740(vwr),1463(s),1412(w),15SO(m),
1360(vw),1344(w),1295(w),1250(w),
1180(w) 1152(w),1082(w) 1050(v ),
1025(vw),1005(Qw) 965(w 0,858(w,*),
850(w,sh) ,772(vw) ,748(vw) ,678(w,b),
590(w),505(w)








Table 1 (cont'd)


(n-CHE9) SbC12
Neat


[(n-C H9) 3Sb(Cl)] 2 i
Nujol


[E(-CH9) Sb(C1)] 20
Carbon disulfide,
Nujol


(C6H5)3Sb
Nujol


(C6H5) SbCl2
iuj ol

[(C6:5 ) Sb(Cl)] 2
Nuj ol





[(C 6 ) Sb(C1)]20
Nuj ol


2970(vs),2940(vs),2880(s),2740(v-),
1468(s),14l10(m),1388(m),1350(w),
1295(w),1255() ,1170(m),1095(m),
1048(w),1005(vw),960(vw ),890(n),
860(w),760(w),712(m),615(vw),512(vw)
3162(m),2181(w),1582(w b),1595(s),
1252(w,b),1164(s),1082(s),1030(m),
1002(w,sh),962(vw),883(m),768(vs),
736(vs) ,698(vs) ,615(vw-) ,511(vw)
2965(vs),2930(vs),2870(s),1572(vw,b),
1405(m),1343(m),1294(m) ,1253(vw),
1181(s),1165(s),1081(m),1028(m),
994(w,sh),885(s),855(m,sh),770(vs),
743(vs),693(vs) 620(w),562(w),524(w),
460(vw,b),400(w)-,260(w)


3060(w),30o40(w),1960(vw,b) ,188C(
1820(vw b),1572(w),1475(m),1428(
1328(vw ,1295(w) ,1178() ,1150(w)
1060(n) ,1012(w),992(w),900(w,),
850(vw),721(vs),689(vs),450(m)


vw,b),
s),
,


3050(vw),1572(w),1475(s),1450(vs),
1326(w),1300(w) 1172(w),1155(w),
1053(w), 1012(w) ,990(m),740(m),
725(vs) ,678(s),450(m) ,277(m)
3140(w),3070(vw, sh),5040(m),1570(m),
1475(s) 1430(vs),1329(m),1502(m),
1268(vw) 1180 (m),1157(m) ,1090(-),
1061(s),1019(s),995(vs),985(w)
975(w),969(w),915(m),880 (vw,sh),
850(w),840(vw,sh),765(vs),735(vs),
690(vs),662(m,sh) 655(w,sh),612(w),
454(vs,sh), ~47(vs), 385(vw),365(vw,sh),
302(w,sh),285(m)
3044(w) ,1968(vw),1891(w) ,1824(vw)),
1780(vw) ,1659(vw) ,1578(w) ,1482(s),
14L4(s.sh) ,1456(vs),1353(w) ,1307(u),
1244(vw),1177(m) ,115(w) ,1058(m),
1018(m),996(s),915(w) 851(vw))
840(vw),768(vs),744(s),731(vs),
690(vs),661(vw,),653(vw),611(w),
456(s),448(s),588(vw),305(w,sh),
290(m),280(m,sh)









Table 1 (cont'd)


[(CHS )3Sb(-T02) ]20
Kel-F, Nujol


(C6H )3SbO
Nujol


(C6H5)3SbO-0.3 H20
Nujol


3045(w) 22L0(w),1950(vw),1885(vwt),
1815(vw),1660(vw),1575(w),1510(m,sh),
1492(vs),1475(m) ,142(s),1335(w),
1305(w,sh),1280(vs),1185(w),1160(vw),
1064(n),1020(m),995(s),975(vs),
915(vw) ,840(v,),802(w) 740(vs),
708(vs),690(vs) 4,55(vs ,445(s,sh),
380(m),300(w,sh5,280(w,b)
3065(w sh),3045(m),1945(,v),1878(w),
1808(w) 1760(vw) 1570(w),1478(s),
1430((vs) ,150(vw ,1305(w),1260(vw),
1178(vw),1155(vw) ,1074(s) ,1063(m),
1022(s) ,998(s) 967(vw) 917(w),
850(vw),743(vs) 728(vs),693(vs),
660(vs,b),617(w),463(s),447(vs),
305(m,sh),293(m),278(m)
3135(v.w) ,5065(m,sh) ,045(m) ,1950(vw),
1890(vw) ,1825(w) ,1575(m) ,1473(s),
1430(s),1330(m),1502(m),1265(rvw),
1180(s),1158(w),105(vs),1021(m),
998(m) ,so(w),860(w),8o50(vw,sh),
733(vs),695(vs),655(vs),616(w),
475(vs),450(vs),300(nm),278(m)


960(vw,b),740(vs)


Sb20
Nujol


a-


as, strong; m,
b, broad; d, doublet;


medium; w, weak; sh, shoulder;
v, very.











resonance analytical spectrometer Model A60-A. Most

spectra were obtained by sweeping slowly through the field

and interchanging the reference with the sample being

studied. In these cases, acetaldehyde or tetramethylsilane

were used as external references. The sample peaks and the

reference peaks are obtained on the same spectrum thereby

facilitating the calculation of the chemical shifts in

approximate T values. Methylene proton shifts in compounds

containing n-propyl and n-butyl groups and phenyl proton

shifts are recorded as ranges.

For most compounds containing phenyl groups, the

spectra were also obtained using benzene as an internal

standard. This facilitates calculation of chemical shifts

of the phenyl protons from the benzene signal and thereby

enables one to observe the relative electron withdrawing

or electron donating ability of the group to which the

phenyl ring is attached. Proton magnetic resonance data

are listed in Table 7; and Figure 68 shows a schematic

diagram of the phenyl proton shifts with respect to benzene.

X-ray powder spectra

The x-ray powder spectra were obtained with a Norelco

X-ray Generator, type 12045, using a wide range goniometer

and a proportional detector. A copper target was used with
0
K Line at 1.541 A. A nickel filter was used.










Manipulative methods

All solvents were stored and transferred in an inert

atmosphere box (D. L. Herring Dri-Lab and Dri-Train combi-

nation) containing dry nitrogen. All glass apparatus was

baked at 1500C. and moved into the dry box while still hot

or else was flamed dry while evacuated. Most chloraminations

were carried out on a vacuum line similar to that shown in

Figure 1, which was flamed before every reaction. The ether

used was peroxide-free.

The anhydrous ether solution of ammonia-free

chloramine was introduced into a special tube flask in vacuo.

The flask was equipped with a vacuum line adapter to insure

that the solution was never exposed to the atmosphere before

being used. The solution was then distilled onto the

stibine taking care to leave the last drop or two to avoid

decomposition of the chloramine. It has been demonstrated

in this laboratory that the majority of the chloramine does

not distill until about the last five milliliters. This is

clearly shown by curves A and 3 of Figure 2 in which a

forty milliliter sample of 0.054 H chloramine was distilled

to the last 0.1 milliliter. The progress of the distilla-

tion was followed by collecting each five milliliters of

distillate and determining the millimoles of chloramine in

that individual increment. These results are shown by

curve A. The total millimoles of chloramine distilled,








































*vacuum pump


vacuum pum]


Fig. 1.-Vacuum line.


vacuum

pump
and
McLeod
gauge









1.6





1.4


1.2



rn

0
01.0


,-


4- 0.8


-I


0.6

0



0.4





0.2







5 10 15 20 25 30 35 40
Volume (ml)
Fig. 2.-Distillation curve for ammonia-free chloramine.










which was obtained by the addition of all the preceding

increments, is represented by curve B.

Chloramine decomposes to some extent during the

filtration through anhydrous copper sulfate and during the

distillation process. Yields of ammonia-free chloramine

ranging from 40 to 70 per cent have been obtained by the

process described above. The factors which influence the

decomposition process are not well understood. However, it

is possible that the decomposition is facilitated by minute

particles of anhydrous copper sulfate that come through the

glass frit during the filtration, since freshly distilled

ammonia-free chloramine can be redistilled to dryness with

a 90 to 95 per cent recovery of chloramine in the distillate.

Synthesis of trialkylstibines

Trialkyl- and triarylstibines generally have been

prepared by the Grignard method (8,9,15). Recently, Stamm

and Breindel (16) discovered a novel method for the prepa-

ration of the trialkylstibines using antimony(III) oxide

and the appropriate trialkylaluminum. However, they did

not report the preparation of trimethyl- or tri-n-propyl-

stibines. We have applied their method to these compounds.

The reactions were always carried out in a dry box and the

trialkylaluminum reagent was not distilled before use.









Trimethylstibine and trimethyldibromostibane

5(C) )A1 + Sb205 = 2(CH ) Sb + 3CE A10

A n-hexane solution of trimethylaluminum, 0.3 mole,

was added dropwise with vigorous stirring to a n-hexane

slurry of antimony(III) oxide, O.1 mole. The total n-

hexane used was 100 milliliters and the addition took

approximately five hours. After the addition was complete,

the contents of the flask were heated to 600C. for an

additional two hours and then allowed to cool over night.

Efficient stirring is a critical factor in this reaction.

The volatile material was distilled at atmospheric

pressure and the fraction boiling under 800C. was then

treated with a carbon tetrachloride solution of bromine.

This produced 49.7 grains of trimethyldibromostibane which

melted at 185-186.5C. (dec.) [Lit. (17) m.p. 200C.]. The

yield based on antimony(III) oxide was 76 per cent of theory.

The infrared spectrum of trimethyldibromostibane is

shown in Figure 3.

No analytical data were obtained as this is a well

characterized compound (13,17).

The proton magnetic resonance spectrum of trimethyl-

dibromostibane is shown in Figure 4. The spectrum consists

of one peak which is attributed to the methyl protons. The

chemical shift value is listed in Table 7.


































900 800 600 400 300 cm-

Fig. 3.-Infrared spectrum of (CH3)3SbBr2.























































Fig. 4.-Proton magnetic resonance spectrum of (CH )3SbBr2.









Trimethylstibine is obtained from the dibromo com-

pound in low yield by reacting it with powdered zinc (18)

in an o
at 763 mm.

The infrared spectrum of trimethylstibine is shown

in Figure 5.

The proton magnetic resonance spectrum was not

obtained.

Tri-n-propylstibine

(n-C-H 7)3Al + Sb 20 0 2(n-C3H7) Sb + 3n-C 3HA10

Tri-n-propylaluminum was reacted with antimony(III)

oxide in the same manner as that described for trimethyl-

stibine. Upon completion of the initial reaction, the

n-hexane was removed by atmospheric distillation and then

tri-n-propylstibine was vacuum distilled from the reaction

flask. Tri-n-propylstibine boils at 95-95oC. at 15.5 mm

[Lit. (19) b.p. 1100C. (39 mm)]. The yield was 41 per cent

of theory based on the above equation.

Figure 6 shows the infrared spectrum of tri-n-

propylstibine.

The proton magnetic resonance spectrum of tri-n-

propylstibine was not obtained.

Triethylstibine

3(C2H5)3A1 + Sb203 2(C2H ) Sb + 3C2H5A10








































1400 1200


800 600 cm-


Fig. 5.-Infrared spectrum of (CH3)3Sb.
R)
ro






































3000 2800


-1
1400 1200 1000 800 600 cm1
Fig. 6.-Infrared spectrum of (n-C3H7)3Sb.









Triethylstibine was prepared by the method of Stamm

and Breindel (16) and worked up in the same manner as that

described for tri-n-propylstibine.
The infrared spectrum of triethylstibine is shown in

Figure 7.

The proton magnetic resonance spectrum of triethyl-

stibine was not obtained.

Ammonia-free chloramination of some trialkylstibines and
triphenylstibine

Trialkylstibines and triphenylstibine react with

ammonia-free chloramine to form iminobis-(trialkylchloro-

stibanes) and iminobis-(triphenylchlorostibane). The re-

action is thought to proceed according to the following

equations:

R Sb + NH2C1 R Sb(iNH2)Cl

2R Sb( iH2 )Cl [R Sb(C1)]2 TNH + NHi

A side reaction is observed in certain cases in which tri-

alkyl- or triphenyldichlorostibane is produced in variable

yields. This reaction is thought to proceed according to

the following equation:

R Sb(NH2)C1 + T:2C1- R SbC12 + 1/5N2 + 5/3_7

Iminobis-(trimethylchloroszibane)

2(CH ) Sb + 2TM2C1 [(CH ) Sb(Cl)]2H +

(CH) 3Sb(ITH2)C1 + NH2C1 (CH ) SbC12 + 1/N + L/5: 7







































3000 2800 1400 1200 1000 800 600 cm-M

Fig. 7.-Infrared spectrum of (C2H5)3Sb.
-r










Trimethylstibine,. 4.49 mmoles, was distilled from

calcium hydride into a tube flask equipped with a stirring

bar. Twenty-seven milliliters of a 0.19 molar ethereal

solution of chloramine was then slowly distilled into the

flask with stirring. The temperature was maintained at

-780C. throughout the transfer, and reaction was evident.

The solid and solvent became yellow and gas evolution was

noticeable as the flask was warmed to room temperature.

The flask was maintained at this temperature for 80 minutes,

after which the ether was removed by distillation. The

non-ccndensible gas formed during the reaction was estimated

to be less than 0.5 mmole. The ether was treated with

gaseous hydrogen chloride, which produced 0.17 gram of

ammonium chloride. This corresponds to 3.18 mmoles of

ammonia. No unreacted trimethylstibine was detected. This

indicates that chloramine was in excess and explains why

more ammonium chloride was found than theory predicts.

The sealed flask was transferred to a dry box and

the crude product, 0.98 gram, was treated with four 5

milliliter portions of boiling toluene. The insoluble solid

(A) was dried in vacuo. Product (A) decomposed to a metallic

gray solid and a volatile reactive liquid when heated above

2000C., and readily evolved ammonia when exposed to the

atmosphere. The yield was 0.67 gram which was 71 per cent

of theory based on the above equations.








Iminobis-(trimethylchlorostibane) is slightly

soluble in chloroform and boiling toluene and insoluble in

a variety of other organic solvents. The infrared spectrum

of iminobis-(trimethylchlorostibane) is shown in Figure 8.

Anal. of product (A). Calcd. for [(CH3) Sb(Cl)]2NH:

C, 17.17; H, 4.56; N, 3.54; Sb, 58.05; Cl, 16.90. Found:

C, 18.13; H, 4.79; N, 3.69; Sb, 58.81; Cl, 17.14.

The toluene wash liquid was evaporated to dryness

leaving 0.27 gram of a white solid (B) as residue. The

material decomposed around 2200C. Product (B) appears to

be a mixture of trimethyldichlorostibane (64.4 per cent),

melting point 2300C. (dec.), and iminobis-(trimethylchloro-

stibane) (35.6 per cent) which decomposes at temperatures

above 2000C. The infrared spectrum was consistent with this

assumption. The total yield of trimethyldichlorostibane

was 16.2 per cent of theory. The iminobis-(trimethylchloro-

stibane) in the above mixture is difficult to separate and

separation is not feasible in most cases. The combined

amounts of the imino compound in products (A) and (B) cor-

responds to a total yield of 81.2 per cent of theory.

The proton magnetic resonance spectrum of iminobis-

(trimethylchlorostibane) is shown in Figure 9. The

complexity of the spectrum probably results from complex

formation with the chloroform which was used as solvent. A

peak resulting from the proton on the nitrogen could not be

found.





































3200 1400 1200 1000 800 600 cm
Fig. 8.-Infrared spectrum of [(CH3)3Sb(C1)]2NH.
rO












































Fig. 9.-Proton magnetic resonance spectrum of [(CH3 )Sb(C1)] NH.


-j










Low-temperature reaction of trimethylstibine with ammonia-
free chloramine

Trimethylstibine, 2.1 mmoles, was distilled from

calcium hydride into the vacuum line. Five milliliters of

a 0.45 molar ethereal solution of chloramine was condensed

onto the stibine at -780C. and allowed to react at this

temperature for three hours. The temperature was then

allowed to rise to -45oC. at which time the volatile ma-

terial, which includes any ammonia produced by a condensa-

tion reaction, was removed. Dry toluene was condensed onto

the residual white solid at -78C. and then 4.2 mmoles of

dry hydrogen chloride gas was condensed into the flask.

The contents of the flask were stirred for one hour at this

temperature and then allowed to come to room temperature.

The volatile material was removed from the flask by vacuum

and fractionated. A total of 0.92 mole of gaseous hydrogen

chloride was consumed in the reaction.

The residue in the reaction flask weighed approxi-

mately 0.13 gram. Analysis of this solid gave an Sb:N:Cl

ratio of 1.9:1.0:5.1. Therefore the material that reacted

with gaseous hydrogen chloride must be some species with

the same Sb:N:Cl ratio as iminobis-(trimethylchlorostibane),

but not necessarily this compound. The reaction might

proceed according to an equation similar to the following:









[(CH )3Sb(C1)12NH() + 3ECl -(g 2(CH 3)SbCl2(s)

+ NH Cl(s)

Sb:N:Cl ratio in product mixture: 2:1:5

Had the reactive species been (CH3)3Sb(NH2)C1, the Sb:N:C1

ratio would have been 1:1:3.

The unreacted stibine was accounted for as trimethyl-

stibine oxide.

Iminobis-(triethylchlorostibane)

2(C2H5)3Sb + 2N1H2C1 [(C2H ) Sb(Cl)]2 T + NH

Triethylstibine, 3.1 mmoles, was introduced into a

vacuum line and degassed twice. Fifty milliliters of a

0.13 molar ethereal solution of chloramine was slowly trans-

ferred onto the stibine with stirring at -780C. The material

was warmed to room temperature and stirred for two hours.

During this time a white solid formed. The solvent was

removed from the flask by vacuum and the sealed apparatus

was transferred into an inert atmosphere box. The crude

material was washed with several small portions of hot

cyclohexane and dried in vacuum. The material melted at

126-129C. to a clear liquid. A total of 0.64 gram was

obtained which was 87 per cent of theory based on the above

equation.

Iminobis-(triethylchlorostibane) is soluble in hot

benzene and chloroform and is insoluble in ethyl and iso-










propyl ethers, n-hexane and cyclohexane. The melting point

can be improved to 128-1290C. by recrystallization from

benzene, but a large portion of the compound is decomposed

in the process. Figure 10 shows the infrared spectrum of

iminobis-(triethylchlorostibane).

Anal. Calcd. for [(C2H5)3Sb(Cl)] NH: C, 28.61; H,

6.20; N, 2.78; Sb, 483.5; Cl, 14.08; MW, 504. Found: C,

28.81; H, 6.12; N, 2.75; Sb, 48.16; Cl, 14.51; MW, 412.

The proton magnetic resonance spectrum of iminobis-

(triethylchlorostibane) is shown in Figure 11. Peak A

results from the protons of the methylene group, peak A'

from the protons of the methylene group of the hydrolysis

product hydrolysiss was brought about by water in the

deutero-chloroform), and peak B from the protons of the

methyl group. The methyl protons of the hydrolysis product

are hidden under peak B. The imino proton peak could not be

resolved.

Iminobis-(tri-n-propylchlorostibane)

2(n-CH 7) Sb + 2Ni2C1 [(n-C H7 )Sb(Cl)]2NH + N3
9 7 3 3 7 2 3
Tri-n-propylstibine, 2.4 mmoles, was introduced into

a vacuum line and degassed twice. Forty milliliters of a

0.07 molar ethereal solution of chloramine was slowly con-

densed onto the stibine with stirring at -780C. The liquid

was stirred at this temperature for one hour and then warmed




































1200


000 800 600 cm-1
1000 800 600 cm~


Fig. 10.-Infrared spectrum of C(C2H5)3Sb(Cl)]2NH.
2 5) 3


1400































ig. A A' e sm of

Pig. 11.-Proton magnetic resonance spectrum of [(C2 5


]2NH.










to room temperature and allowed to react for an additional

two hours. The reaction product was soluble in ether at

room temperature. The solvent was removed by vacuum and

the sealed flask was transferred into an inert atmosphere

box. The crude product was washed with several small

portions of n-hexane and dried by vacuum. The yield was

0.51 gram of a white solid (72 per cent of theory). The

unrecrystallized solid melted at 87-940C. Low temperature

recrystallization from ether yields a material which melts

at 83-850C. The wash solvent yielded an additional portion

of product which raised the yield to 76.5 per cent of theory

based on the above equation.

Iminobis-(tri-n-propylchlorostibane) is soluble in

ethyl ether and chloroform and slightly soluble in n-hexane.

Heating the compound in various solvents causes decomposi-

tion and the formation of an oil. The infrared spectra of

the crude and recrystallized product are very similar and

the spectrum of the latter is shown in Figure 12.

Anal. Calcd. for [(n-C 3 7) 3Sb(1C)]N2 C, 56.77;

H, 7.37; N, 2.58; Sb, 41.42; Cl, 12.06. Found: (recrystal-

lized) C, 56.58; H, 7.22; N, 2.17; Sb, 42.13; Cl, 11.99;

(crude) C, 36.35; H, 7.14; N, 2.67; Sb, 41.29; Cl, 11.69.

Figure 13 shows the proton magnetic resonance spectrum

of iminobis-(tri-n-propylchlorostibane). Peak A is attributed

to the methylene protons and peak B to the methyl protons.

The imino proton could not be resolved.




































3200 1400 1200 1000 800 600 cm

Fig. 12.-Infrared spectrum of [(n-C3H7) Sb(C1)]2 IH.
p-







































A B


Fig. 13.-Proton magnetic resonance spectrum of [(n-C3H7) Sb(Cl) ]2NH.

kyJ











Iminobis-(tri-n-butylchlorostibane)

2(n-C4H 9)3b + 2NH2C1- [(n-C4H9) Sb(Cl)]2IT + NH

The effluent gases from the chloramine generator (20)

were passed directly through pure tri-n-butylstibine, 0.1

mole, for 1.4 hours. The temperature of the liquid rose

to about 600C. during this period and it became very vis-

cous. The liquid was filtered and stirred under vacuum

for twelve hours during which time a gas was evolved and

the material partially solidified. The semi-solid substance

was spread between two porous plates in a dry inert atmos-

phere and ground for about fifteen minutes. This process

was repeated until a flaky white solid was obtained which

melted at 49-500C. The total yield was 17.7 grams which

was 51 per cent of theory based on the above equation.

Vacuum-line technique using ammonia-free chlorsmine

yields the same product in about 90 per cent yield. How-

ever, the presence of unreacted stibine causes the formation

of an oil from which the product is not readily separated.

The infrared spectrum of the oil is consistent with that to

be expected for the above product diluted with starting

material.

Iminobis-(tri-n-butylchlorostibane) is soluble in

most of the common organic solvents. The material cannot

be stored for long periods of time as it slowly decomposes

to a yellow oil. The infrared spectrum of iminobis-(tri-









n-butylchlorostibane) is shown in Figure 14. For compari-

son the infrared spectrum of tri-n-butylstibine is shown

in Figure 15.

Anal. Calcd. for [(n-C4H9)3Sb(Cl)]2NH: C, 42.88;

H, 8.25; N, 2.08; Sb, 36.23; C1, 10.55; HW, 672. Found:

C, 42.72; H, 8.13; N, 1.80; Sb, 36.24; Cl, 10.51; NW, 549.

Figure 16 shows the proton magnetic resonance

spectrum of iminobis-(tri-n-butylchlorostibane). Peak A

results from all the methylene protons and peak B from the

methyl protons. The absorption resulting from the lone

imino proton was not found. The proton magnetic resonance

spectrum of tri-n-butylstibine is shown in Figure 17.

Iminobis-(triDhenylchlorostibane)
2(C6H5) Sb + 2NH2C1l [(C6H5)3Sb(Cl)]2NH + NT3

(C6E5)3Sb(NH2)Cl + NH2Cl (C6H5)3SbCl2 + 1/3N2

+ 4/3NH3

In a typical experiment, 39 milliliters of 0.025 H

ammonia-free chloramine was condensed into an ethereal

solution (50 ml) of 2.14 mmoles of triphenylstibine at

liquid nitrogen temperature, and the temperature of the

mixture allowed to rise. A white solid formed and the

ether became light yellow in color at just under room

temperature. Gas evolution was also observed at this point.

The reaction was allowed to continue for five hours, after
































3300 320'0 1o00 1200 1000 800 60
Fig. 14.-Infrared spectrum of [(n-C4H)3 Sb(C1)]2NH.



































1200


1000


800


I I


, I


3000 2800


1400


600 500 c-1
600 500 cm


Fig. 15.-Infrared spectrum of (n-C4H9) Sb.


ffvnv Fr


I


I |






























Fig. 16.-Proton magnetic resonance spectrum of [(n-CH9)3Sb(C1)]2NH.













































Fig. 17.-Proton magnetic resonance spectrum of (n-C H9)3Sb.

H










which the solvent was removed by vacuum. A non-condensible

gas was formed during the reaction (yield 0.075 mmole). A

molecular weight determination showed the gas to be nitrogen.

The solvent was then treated with gaseous hydrogen chloride,

which produced a total of 1.49 mmoles of ammonium chloride.

The sealed reaction flask was transferred into a dry

box and the crude product was washed with 0.5 milliliter

portions of dry carbon tetrachloride until the insoluble

solid gave a melting point of 219-220.50C. Yields of

iminobis-(triphenylchlorostibane) of 55 to 71 per cent and

of triphenyldichlorostibane of 25 to 43 per cent of theory

were obtained in a series of experiments using various mole

ratios and concentrations of reactants.

Iminobis-(triphenylchlorostibane) is soluble in

chloroform and hot benzene and slightly soluble in ether

and carbon tetrachloride. It does not react with gaseous

or liquid ammonia, nor is it readily susceptible to

hydrolysis in the atmosphere in the dry state. The infra-

red spectrum is shown in Figure 18.

Anal. Calcd. for [C(CH)Sb(Cl)]2H: C, 54.59; H,

3.94; N, 1.77; Cl, 8.95. Found: C, 54.26; H, 4.15; N,
1.81; Cl, 9.15.

The carbon tetrachloride wash liquid was evaporated

to dryness leaving 0.35 gram of an oil as residue. The oil

was extracted with a small portion of petroleum ether, which







-H


/ V








S I I I I I
5100 1400 1200 1000 800 600 400 cm
Fig. 18.-Infrared spectrum of [(C6H)5 Sb(C1)]2 H.










dissolves triphenylstibine. The insoluble residue was

identified as triphenyldichlorostibane which melts at 143-

1440C. A total of 0.47 mmole was obtained. Triphenyl-

stibine, 0.31 mmole, was recovered from the petroleum ether.

The infrared spectra of triphenylstibine and triphenyldi-

chlorostibane are shown in Figures 19 and 20 respectively.

The proton magnetic resonance spectrum of iminobis-

(triphenylchlorostibane) is shown in Figure 21. Peaks A

and A' are assigned to the phenyl protons; peak A to the

ortho protons and peak A' to the meta and para protons.

The spectrum was also taken with respect to benzene which

was used as an internal standard. The ortho proton signal

is shifted -18 cps from the benzene signal, whereas the meta

and para proton signals are not significantly changed from

benzene. A downfield shift from benzene is recorded as

negative values and an upfield shift as positive values.

The signal for the imino proton is probably weak and broad

and difficult to observe, and in some cases, it is probably

overlapped by the phenyl proton absorptions.

The proton magnetic resonance spectrum of triphenyl-

stibine is shown in Figure 22. The chemical shift values

for the ortho, meta and para protons are similar and as a

result, the ortho proton signal is not significantly moved

downfield from that of the meta and para protons. One can

see the typical ortho proton pattern of four peaks of





























I I I I I I
1800 1600 1400 1200 1000 800
Fig. 19.-Infrared spectrum of (C6H5)3Sb.




[-H-- )-


I

I i I I
1400 1200 1000 800 450 275 cm
Fig. 20.-Infrared spectrum of (C6H )3SbC12.







































Fig. 21.-Proton magnetic resonance spectrum of [(C6H5) Sb(C1)]2NH.

p




























































Fig. 22.-Proton magnetic resonance spectrum of (CE-) Sb.
ZD 0 5 -1









increasing height on the downfield side of the phenyl

signal. When the spectrum was taken with respect to benzene

it was found that the phenyl signal was almost symmetrically

situated around the benzene signal.

Hydrolysis of the ammonia-free chloramination products

The alkyl chloramination products are readily

hydrolyzed by exposure to moisture. Ammonia evolution is

immediately noticeable. Dry iminobis-(triphenylchloro-

stibane) does not hydrolyze as readily as the alkyl deriva-

tives. Hydrolysis probably occurs according to the follow-

ing equation:

[R3Sb(C1)]2NH + H20 [R Sb(Cl)]20 + N3

Oxybis-(trimethylchlorostibane)

[(CH )3Sb(Cl)]2T.1 + H20 [(CH3)3Sb(Cl)]20 + N:3

Iminobis-(trimethylchlorostibane), 0.85 mole, was

ground and exposed to the atmosphere until ammonia evolution

ceased. There was no noticeable weight change. The re-

sulting compound decomposed at temperatures above 2000C. to

a white solid and a volatile, highly reactive, liquid. The

material can be recrystallized from alcohol. Large crystals

of this compound tend to break up into powder at about

2200C. The yield was 100 per cent of theory based on the

above equation (not recrystallized).










Oxybis-(trimethylchlorostibane) is soluble in water

and hot alcohol and slightly soluble in chloroform. The

infrared spectrum of oxybis-(trimethylchlorostibane) is

shown in Figure 23 and. has been discussed in a previous

publication (13).

Anal. Calcd. for C(CH3)3Sb(Cl)]20: Cl, 16.85.

Found: Cl, 16.66.

The proton magnetic resonance spectrum of oxybis-

(trimethylchlorostibane) is shown in Figures 24 (CDC13) and

25 (H20). The spectrum in which chloroform was used as

solvent is complex and probably results from a reaction

between the compound and solvent. This apparently does

not happen when water is used as a solvent, as a lone peak

is observed which results from the methyl protons.

Oxybis-(triethylchlorostibane)

[(C2H 5) b(Cl)]2NH + H0 [(CCH5)3Sb(Cl)]20 + NH

In a typical experiment, 1.23 mmoles of iminobis-

(triethylchlorostibane) was dissolved in a methanol-water

mixture and stirred for one hour. The solvent was removed

by vacuum leaving an oil as residue. The oil was dissolved

in boiling cyclohexane and upon cooling to room temperature

white plate-like crystals formed. The yield was 0.62 gram

which was 100 per cent of theory based on the above equation.

The material melted at 179-1800C.






































400 300cm-1
1400 1200 1000 800 600 400 300 cm

Fig. 23.-Infrared spectrum of [(CH3)Sb(C1)]20.
I-3













































Fig. 24.-Proton magnetic resonance spectrum of [(CH )3Sb(C1)]20 (CDC13).

VI1
N)













































Fig. 25.-Proton magnetic resonance spectrum of [(CH3)3Sb(C1)]20
(H20).










Oxybis-(triethylchlorostibane) is soluble in water,

alcohol, benzene and hot cyclohexane and is insoluble in

various ethers. It is hygroscopic, readily sublimes in

vacuum, and decomposes when heated above its melting point

at atmospheric pressure. The infrared spectrum is shown in

Figure 26.

Anal. Calcd. for [(C2H5) Sb(C1)]20: C, 28.54; H,

5.99; Cl, 14.04; N!, 505. Found: C, 28.92; H, 5.92; Cl,
14.18; Mw, 497.

The proton magnetic resonance spectrum of oxybis-

(triethylchlorostibane) is shown in Figure 27. Peak A

results from the methylene protons and peak B from the

methyl protons.

Oxybis-(tri-n-propylchlorostibane)

[(n-C H7)3Sb(Cl)] 2N + H20 C[(n-CH7) Sb(Cl)] 2 + NH3

Iminobis-(tri-n-propylchlorostibane), 0.49 mmole,

was exposed to the atmosphere and allowed to remain until

ammonia evolution ceased. The solid was recrystallized

from n-hexane. A total of 0.24 gram was obtained which was

84 per cent of theory based on the above equation. The

compound melted at 98-1000C.

Oxybis-(tri-n-propylchlorostibane) is soluble in

benzene, chloroform and hot n-hexane and is insoluble in

water. An x-ray powder pattern was obtained using a sweep




































I I I I I -
1400 1200 1000 800 600 400 300 cm

Fig. 26.-Infrared spectrum of [(C2H5)3Sb(Cl)]20.








































Fig. 27.-Proton magnetic resonance spectrum of [(C2H5)3Sb(C1)]20.
V1








rate of one-fourth of a degree per minute. The angles and

relative intensities are listed in Table 2. The relative

intensities were calculated from measurements taken

directly from the recorded spectrum.


TABLE 2

X-RAY POWDER DATA FOR [(n-C3H7)3Sb(Cl)]20

Angle, ) I Angle, O I

5.11 10.0 11.86 0.36
6.14 2.12 12.68 0.67
9.46 1.45 13.96 2.07
9.61 0.62 14.11 0.52
10.23 3.01 15.04 0.67
10.37 0.95 15.42 0.98
10.93 1.24 16.41 0.41
11.52 0.62 18.75 0.36
11.48 0.57 18.88 0.67


The infrared spectrum of oxybis-(tri-n-propylchlorostibane)

is shown in Figure 28.

Anal. Calcd. for [(n-CH7) 3Sb(C1)]20: C, 56.71; H,

7.19; Sb, 41.34; Cl, 12.04; MW, 589. Found: C, 36.75; H,

7.16; Sb, 41.39; Cl, 11.75; Hd, 635.
The proton magnetic resonance spectrum of oxybis-

(tri-n-propylchlorostibane) is shown in Figure 29. Peak A

is attributed to the methylene protons and peak B to the

methyl protons.




































F 1 I I I I I c
1400 1200 1000 800 600 400 300 cm

Fig. 28.-Infrared spectrum of [(n-C 3H)3Sb(C1)]20.






























Fig. 29.-Proton magnetic resonance spectrum of C(n-C3H7)3Sb(C1)]20.










Oxybi s-(tri-n-butylchlorostibane)

[(n-CH9) Sb(Cl)]2NH + H20 [-(n-C 9) Sb(Cl)]20 + NH3

Iminobis-(tri-n-butylchlorostibane), 0.28 mmole, was

exposed to the atmosphere until ammonia evolution was

complete. The product was compressed between porous plates

until a flaky white solid was obtained with a melting point

of 52-540C. The yield was 0.16 gram which was 85 per cent
of theory based on the above equation.

Oxybis-(tri-n-butylchlorostibane) is soluble in most

common organic solvents and water. The infrared spectrum

of this compound is shown in Figure 30.

Anal. Calcd. for [(n-C H g)Sb(Cl)]20: C, 42.83; H,

8.09; Cl, 10.54. Found: C, 43.03; H, 8.11; Cl, 10.60.

The proton magnetic resonance spectrum was not

obtained for this compound.

Oxybis-(trizhenylchlorostibane)

[(C6H5)3Sb(Cl)]2NH + H20 [(C6H5)3Sb(Cl)]20 + NH3

Iminobis-(triphenylchlorostibane), 0.56 mmole, was

suspended in wet acetone and warmed until ammonia evolution

ceased. The solvent was removed by vacuum and the residual

white solid was recrystallized from benzene to yield 0.42

gram of a solid which melted at 219-2220C. [Lit. (12) m.p.

2220C.j. A mixed melting point determination with an

authentic sample of oxybis-(triphe-ylchlorostibane) showed

































I 5 I -1
400 300 cm


Fig. 30.-Infrared spectrum of [(n-C H9) Sb(C1)]20.











no depression and the solid did not release ammonia when

treated with base. The infrared spectrum is shown in

Figure 31.

Analytical data were not obtained.

Figure 32 shows the proton magnetic resonance

spectrum of o;cybis-(triphenylchlorostibane). Peak A is

assigned to the ortho protons of the phenyl groups and peak

A' to the meta and para protons of the phenyl groups. The

spectrum was taken using benzene as an internal standard

and it was found that the ortho proton signal was shifted

-21.2 cps from the benzene signal. The meta and para

proton signal was not shifted significantly from that of

benzene.

Some reactions of organoantimony(V) compounds

A variety of miscellaneous reactions of some organo-

antimony(V) compounds were carried out in order to obtain

products from which infrared and proton magnetic resonance

data could be obtained. In most cases yield data were not

obtained.

Pyrolysis of oxybis-(trimethylchlorostibane)

5[(CH 3)Sb(C1)] 20 -A Sb20 + 4(CH3)3Sb + 6CH3C1

Oxybis-(trimethylchlorostibane), 2.02 mmoles, was

placed in a small flask equipped with a take-off head and

receiver. The apparatus was thoroughly evacuated and then
































1400 1200 1000 800 600 400 300 cm

Fig. 31.-Infrared spectrum of [(C6H5)3Sb(C) ]20.
















































A A'


Fig. 32.-Proton magnetic resonance spectru- of
[(C6H5) Sb(Cl)]20.









brought to atmospheric pressure with dry nitrogen. The

flask was slowly heated until a maximum temperature of 2600C.

was reached and held for one half hour. During this time a

liquid distilled and was identified as trimethylstibine by

vapor pressure measurements (21). A total of 0.32 gram was

obtained which was 71.4 per cent of theory.

The solid residue was identified as antimony(III)

oxide by comparison of its infrared spectrum with that of

an authentic sample of the compound (22). The residue

weighed 0.18 gram which was 92.6 per cent of theory based

on the above equation. Methyl chloride was assumed to be

the other product, but was not measured in this experiment.

The infrared spectrum of antimony(III) oxide is shown

in Figure 33.

Trimethyldichlorostibane

[(CH ) Sb(Cl)]20 + 2Cl(conc.) 2(CH )3SbC12 + H20

An aqueous solution of oxybis-(trimethylchlorostibane),

1.31 mmole, was treated with an excess of concentrated

hydrochloric acid. A white compound, insoluble in water,

was formed and was recrystallized from the acidic reaction

solvent. The yield was 0.49 gram (79 per cent of theory

based on the above equation). The material melted at 230-

230.50C. (dec.) [Lit. (17) m.p. 229-230C. (dec.)].

Trimethyldichloros-ibane is soluble in chloroform,

boiling water and boiling toluene. The infrared spectrum of



































1000 800 cm-1

Fig. 33.-Infrared spectrum of Sb20 .









trimethyldichlorostibane is shown in Figure 34 and is

consistent with that found in the literature (13).

Anal. Calcd. for (CH ) SbC12: C1, 29.8. Found:

Cl, 29.8.

The proton magnetic resonance spectrum of trimethyl-

dichlorostibane is shown in Figure 35. The single peak

results from the methyl protons. This spectrum is entirely

consistent with the established crystal structure of the

molecule (23), which is trigonal bipyramidal with the methyl

groups in the equatorial positions.

Oxybis-(trimethylnitratostibane)

[(CE ) Sb(C1)]p + 2Ag+ + 2NO [(CH )Sb(ON2)]20

+ 2AgCl

Aqueous silver nitrate was added dropwise to an

aqueous solution of oxybis-(trimethylchlcrostibane) until

precipitation was complete. The resulting silver chloride

was removed by filtration and the solution was evaporated

to dryness. The residual white solid was recrystallized

from alcohol to yield a material that melted at 262C. (dec.).

No yield data were obtained since the compound was prepared

for the purpose of obtaining infrared and proton magnetic

resonance spectra.

Oxybis-(trimethylnitratostibane) is soluble in water

and slightly soluble in chloroform. The infrared spectrum

of this compound is shown in Figure 36. The very strong,




































I I I I I I
1000 800 600 400 300 cm

Fig. 34.-Infrared spectrum of (CH3)3SbC12.















































Fig. 35.-Proton magnetic resonance spectrum of (CH3)3SbCl2.





































I I I I ' -1
'0 1200 1000 800 600 400 300 cm

Fig. 36.-Infrared spectrum of C(CH3) Sb(ON02)]20.
o









broad, peaks at 1480-1380 cm-1 and 1310-1275 cm-1 are

attributed to the v4 and v1 absorption frequencies of the

partially covalent nitrate group (24), which exhibits C2

symmetry. It has been suggested that the degree of split-

ting between v4 and v1 is a measure of covalent character

(25) as long as it exceeds 125 cm-1 (26). Any splitting
less than this value might result from lattice distortion.

Oxybis-(trimethylnitratostibane) has a v4 v1 splitting of

137 cm-1. Also, a strong absorption occurs at 1018 cm-
which is the v2 mode for the covalent nitrato group. The

v6 mode which usually occurs in the 800-781 cm-1 region is

probably overlapped by the strong Sb-O-Sb absorption at
-1
788 cm-.

Anal. Calcd. for [(CE3)3Sb(ON02)]20: C, 15.21; H,

3.83; N, 5.91. Found: C, 15.20; H, 3.90; N, 5.98.

The proton magnetic resonance spectrum of oxybis-

(trimethylnitratostibane) is shown in Figure 37. The single

peak results from the methyl protons. When chloroform was

used as the solvent, three peaks resulted as was the case

with iminobis- and oxybis-(trimethylchlorostibanes).

Trimethyldinitratostibane

(CH ) Sb3r2 + 2Ag+ + 2NO3 (CEH )Sb(ONO + 2AgBr

Trimethyldinitratostibane was prepared by the method

of Long et al. (13) in which an aqueous solution of tri-

methyldibromostibane was reacted with aqueous silver nitrate












until the precipitation of silver bromide was complete.

The solution was freed of silver bromide by filtration and

the water was removed by vacuum. The residual solid was

recrystallized from alcohol. The resulting crystals melted

at 149-1500C. No yield data were obtained.

Trimethyldinitratostibane is soluble in water and

chloroform. The infrared spectrum is shown in Figure 38.

The v4 v1 splitting is 240 cm-1. The spectrum of this

compound was discussed by Long (13) and later by Clark and

Goel (27). Our work agrees quite closely with that of the

latter authors although no special reaction conditions were

maintained.

Anal. Calcd. for (CH3)3Sb(ON02)2: C, 12.39; H,

3.12; N, 9.63. Found: C, 12.25; H, 3.22; N, 9.44.
The proton magnetic resonance spectrum of trimethyl-

dinitratostibane is shown in Figure 39. The lone peak

results from the methyl protons.

Oxybis-(triethylnitratostibane)

[(C2H5) Sb(Cl)]20 + 2Ag+ + 2TO [(C2H )3Sb(0N02)20

+ 2AgCl

An aqueous solution of oxybis-(triethylchlorostibane)

was reacted with an aqueous solution of silver nitrate until

precipitation was complete. The solution was filtered free

of silver chloride and evaporated to dryness by vacuum. The





I i --


2500 1850 1700 1600


-H-


1400


800 550 300 cm


1000


Fig. 38.-Infrared spectrum of (CH 3)Sb(ON02)2.


AI i

n


1*1-






















iJ
Fig. 39.-Proton magnetic resonance spectrum of
(CH3) Sb(ON2O2 .










resulting compound melted with decomposition at 233cC. after

recrystallization from alcohol. No yield data were obtained.

The infrared spectrum of oxybis-(triethylnitrato-

stibane) is shown in Figure 40. The v4 v1 splitting is
11
165 cm-1. Some of the other characteristic absorptions

are partially or completely overlapped by C-H absorptions

and are therefore not observed or occur as shoulders.

Anal. Calcd. for [(C2H5)3Sb(ONO2)]20: C, 25.83;

H, 5.42. Found: C, 26.45; H, 5.78.

Proton magnetic resonance data were not obtained for

this compound.

Tri-n-butyldichlorostibane (28,29,30)

3(n-CH9)3 Sb + 2SbCl3 3(n-C4H) SbC12 + 2Sb

Resublimed antimony(III) chloride, 0.137 mole, was

dissolved in 100 milliliters of dry benzene and slowly added

to tri-n-butylstibine, 0.204 mole, with vigorous stirring in

a dry nitrogen atmosphere. The colorless liquid clouded and

turned yellow, then orange, then brown, and finally black.

The mixture was stirred overnight and then heated to 500C.

for two hours. During this time the black solid turned

metallic gray. The liquid was filtered in a dry box and the

benzene was removed under reduced pressure. The higher

boiling liquid residue was distilled under vacuum. A total

of 61.8 grams of a liquid that boiled at 120-1250C. at



































I I I I I I I i
14-00 1200 1000 800 600 400 300 cm

Fig. 40.-Infrared spectrum of [(C2H5) Sb(ONO)220.










0.14 mm was collected (83 per cent of theory based on the

above equation).

Tri-n-butyldichlorostibane is a colorless, mobile,

liquid which slowly hydrolyzes when exposed to the atmos-

phere. It decomposes to an orange, high-boiling liquid and

a low-boiling liquid when heated over 200C. at 200 mm

pressure. The orange liquid boils at 121-1235C. at 10 mm.

Since compounds of the type R2SbX are commonly prepared by

heating the corresponding R SbX2 (9,18) it is probable that

the orange liquid is di-n-butylchlorostibine. No analytical

data were obtained since the orange compound partially

decomposed upon standing with the deposition of a black

solid. The yield was 89 per cent of theory. The infrared

spectra of tri-n-butyldichlorostibane and di-n-butylchloro-

stibine are shown in Figures 41 and 42, respectively.

Anal. Calcd. for (n-C4H 9)SbC12: C, 59.59; H,

7.48; Cl, 19.48. Found: C, 39.59; H, 7.36; Cl, 19.32.

Proton magnetic resonance data were not obtained for

either of the two compounds.

Triphenyldichlorostibane

[(CH)Sb(C1)]20 +2HC1 excess HCl 2( )SbC
65 (g) excess H20 26 5 2
+ H20

A hot benzene solution of oxybis-(triphenylchloro-

stibane), 5.85 mmoles, was treated with excess gaseous





































I I


1000


800


600 500 cm


Fig. 41.-Infrared spectrum of (n-CqH9) SbC 2.


| I I I


S1400


1200


I


_ 1




































500 cm


1400 1200 1000 800 600

Fig. 42.-Infrared spectrum of (n-C4H9)2SbC1.










hydrogen chloride and then allowed to cool to room tempera-

ture. No crystals appeared at this point indicating that

reaction was complete. About 10 milliliters of alcohol was

added, the solution was heated to boiling, and the benzene

was removed by passing nitrogen directly through the hot

liquid. White needles were obtained by recrystallization

from the alcohol. A total of 2.86 grams of the crystalline

product was obtained which was 87.6 per cent of theory

based on the above equation. The solid melted at 143-1440C.

and showed no depression in the melting point when mixed

with an authentic sample of triphenyldichlorostibane.

Triphenyldichlorostibane is soluble in benzene, hot

ethyl acetate and hot alcohol and slightly soluble in

ether, n-hexane, cyclohexane and carbon tetrachloride. The

infrared spectrum is shown in Figure 20.

Elementary analyses were not required.

The proton magnetic resonance spectrum of triphenyl-

dichlorostibane is shown in Figure 43. The peak labelled A

is assigned to the ortho protons of the phenyl groups and

peak A' to the meta and para protons. The area ratio of A

to A' is approximately 2 to 3 as would be expected. The

spectrum was also taken with respect to internal benzene and

it was found that the ortho proton pattern was shifted

-55.5 cps from the benzene signal and the meta and para

proton pattern was shifted -8.5 cps. This gives some









































Fig. 43.-Proton magnetic resonance spectrum of (C6H5)3SbC12*


[C










insight into the electron withdrawing ability of the

Cl-Sb-Cl group and is in complete agreement with the re-

sults of an x-ray study of this compound (31). It was found

that the crystal structure of triphenyldichlorostibane is

trigonal bipyramidal with the phenyl groups in the equatorial

plane and the chlorine atoms in the axial positions. The

Sb-Cl bond length appears to be somewhat larger than normal

thereby placing a large delta positive charge on antimony

and explaining why the Cl-Sb-Cl group functions as a good

electrophile. It is almost comparable to a nitro group,

which shifts the ortho proton signal -56.9 cps from the

benzene signal (32).

Triphenylstibine oxide (33)

(C6H5)3SbC12 + 20H- (C6H5)3SbO + H20 + 2C1-

An alcoholic solution of triphenyldichlorostibane was

added to a boiling aqueous solution of sodium hydroxide.

A white solid formed immediately. The liquid was boiled

for an additional 30 minutes and then the solid was filtered

free of liquid. The insoluble solid was washed with cold

water until the wash water was neutral and chloride free.

The compound was dried by vacuum and found to melt at 235-

290C. with decomposition. Since the material was prepared

for the purpose of performing an infrared study, no yield

data were obtained.










Anal. Calcd. for (C6H5)3 bO: C, 58.57; H, 4.10.

Found: C, 58.70; H, 4.28.

Triphenylstibine oxide appears to be relatively

insoluble in most common organic solvents. Figure 44 shows

the infrared spectrum of this compound. The peak at 660
-1
cm is attributed to the polymeric Sb-O-Sb absorption.

Attempts to prepare triphenylstibine oxide from

triphenyldichlorostibane by treatment with refluxing water

and vigorous stirring for several days (54) yielded only

oxybis-(triphenylchlorostibane).

The proton magnetic resonance spectrum of triphenyl-

stibine oxide was not obtained.

Triphenylstibine oxide hydrate

(C6H5)3SbO + xH20- (6CH5)3SbO.xH20

Triphenylstibine oxide was treated with boiling,

moist, benzene until a portion of the solid dissolved. The

benzene was filtered free of solid and allowed to slowly

cool thereby producing a white solid. The recrystallized

solid melted at 209-2120C.

The infrared spectrum of triphenylstibine oxide

partial hydrate is shown in Figure 45. The absorption at

655 cm-1 is attributed to the polymeric Sb-O-Sb vibration.

Anal. Calcd. for (C6H5 )SbO-0.3H20: C, 57.79; H,

4.19. Found: C, 57.79; H, 4.20.




































I -1.
1800 1600 1400 1200 1000 800 600 400 300 cm

Fig. 44.-Infrared spectrum of (C6H5)3SbO.






































1800 1600 1400 1200 1000 800 600 400 300 cm

Fig. 45.-Infrared spectrum of (C6H )3SbO-O.5H20.
cn
00











Figure 46 shows the proton magnetic resonance spectrum

of triphenylstibine oxide partial hydrate. The peak labelled

A is assigned to the ortho protons of the phenyl groups and

peak A' to the meta and para protons. The area ratio of A

to A' is approximately 2 to 3. The ortho protons are

shifted -27 cps from the benzene signal while the meta and

para proton pattern fall symmetrically around the benzene

signal. The signal for the protons attached to oxygen was

not observed and is presumed to be overlapped by the phenyl

signal or not resolved from the background.

Oxybis-(triphenylnitratostibane)


2(C6H ) SbC12 + 4AgNO + H20 1.alc [(CH ) Sb(ONO)20

+ 4AgC1 + 2HNO3

Oxybis-(triphenylnitratostibane) was prepared by the

method of IMorgan et al. (8), in which an alcoholic solution

of triphenyldichlorostibane was treated with an alcoholic

solution of silver nitrate. The resulting white solid was

recrystallized from water and found to melt at 2260C. (dec.).

No yield data were obtained.

Figure 47 shows the infrared spectrum of oxybis-

(triphenylnitratostibane). All the characteristic covalent

nitrato-group absorptions are present and the v4 v1

splitting is 220 cm-1 The Sb-O-Sb absorption has apparently

been shifted to a lower wave number such that it is now







88









































A A#

Fig. 46.-Proton magnetic resonance spectrum of
(C H5 )3Sb.0. H20.



































| f I I .
14-00 1200 1000 800 600 400 500 cm

Fig. 47.-Infrared spectrum of [(CgH5 3Sb(ON02)]20










overlapped by the characteristic phenyl absorption in the

740 cm-1 region.

Anal. Calcd. for [(C6H5)3Sb(ON02)]20: C, 51.10;

H, 3.57; N, 3.31. Found: C, 51.00; H, 3.64; N, 3.31.

The proton magnetic resonance spectrum of oxybis-

(triphenylnitratostibane) is shown in Figure 48. The phenyl

absorption is shown as a rather complex signal in which the

chemical shift values for the ortho, meta, and para protons

are similar. The chemical shift from the benzene signal

was not measured.


Discussion


The main purpose of this study was to investigate the

reaction of chloramine with various trialkylstibines and

triphenylstibine. The results clearly establish the

generality of the chloramine-tertiary stibine reaction and

also shows, at least in part, that chloramine reacts with

stibines in a manner analogous to its reaction with amines,

phosphines and arsines. Another fact brought out by this

work is that rigorously anhydrous conditions must be main-

tained at all times as the resulting antimony-nitrogen

compounds rapidly hydrolyze.

The trimethylstibine-ammonia-free chloramine reaction

proceeds quite vigorously at room temperature producing















































Fig. 48.-Proton magnetic resonance spectrum of
[(C H5)3Sb(oNo2)]20.




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