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Adducts of Arsenic andAntimony Trichlorides andAntimony Pentachlorides withβ-KetoaminesR. P. Singh a & A. K. Pandey aa Department of Chemistry , Hindu Degree CollegeZamania , Ghazipur, 232331, U.P., IndiaPublished online: 23 Sep 2006.

To cite this article: R. P. Singh & A. K. Pandey (1992) Adducts of Arsenic andAntimony Trichlorides and Antimony Pentachlorides with β-Ketoamines, Synthesisand Reactivity in Inorganic and Metal-Organic Chemistry, 22:7, 1031-1039, DOI:10.1080/15533179208016609

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SYNTH. REACT. INORG. MET.-ORG. CHEM., 22(7), 1031-1039 (1992)

ADDUCTS OF ARSENIC AND ANTIl43NY TRICHLORIDES AND

ANTIKINy PeNTACHLORXDES WITH /3dWl'OAMINES

R.P. Sin** and A.K. Pandey Department of Chemistry Hindu Degree College Zamaaia, ahaz ipur 232331

U.P., INDIA

ABSTRACT

The prepara t ion and phys ica l properties of t h e adducts of

arsenic and antimony t r i c h l o r i d e and a n t i m n y pentachlor ide

with@-ketoamines of t h e types MCl3.W'CCCHC(NHR) ~e and

Sbc15.MCOCHC(NHR)Me (where M = AS, Sb; R' = Me, Ph; R = Me,

E t , i-Pr) have been descr ibed. The i n f r a r e d spectra of t h e

a d d i t i o n compounds suggested t h a t t h e p-ketoamines are

coordinated t o a r s e n i c ( I I 1 ) through t h e oxygen atom and

antimony (111 and V) through t h e n i t rogen atom of t h e azomethine

group. A l l t h e a d d i t i o n compounds have been found to be i o n i c

in n a t u r e in a c e t o n i t r i l e .

INTRODUCTION

An i n t e r e s t i n g stereochemical behavfour h a s been observed in t h e

complexes of t r a n s i t i o n metals with /3-ketoamlne~'-~. The

chemistry of f3-ketoamine complexes with a r s e n i c and antimony

h a s n o t been i n v e s t i g a t e d , although one would expect new f e a t u r e s

in t h e i r s tereochemistry due t o t h e lone pair of e l e c t r o n s . The

p r e s e n t comnunication reports our attempts to prepare and

c h a r a c t e r i s e t he adducts of a r s e n i c and a n t i m n y t r i c h l o r i d e

and antimony pentachlor ide with fl-ketoandnes.

1031

Copyrignt 8 1992 by Mueel Dekkcr, Inc.

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1032 SINGH AND PANDEY

EXPERIMENTAL

Analv ses

S t r i n g e n t p r e c a u t i o n s were taken t o exc lude m i s t u r e throughout

t h e chemica ls and a p p a r a t u s and also d u r i n g t h e spectral measurements.

p-Ketoamines w e r e prepared by t h e l i t e r a t u r e procedure , Arsenic

t r i c h l o r i d e (B.D.H.) , antimony t r i c h l o r i d e (B.D.H.) and antimony

p e n t a c h l o r i d e (Aldrich) were d i s t i l l e d before use. The metals

a r s e n i c ( I I 1 ) , ant imony(II1) and a n t i m n y ( V ) were determined by

t h e l i t e r a t u r e procedures4. Chlor ine was determined g r a v i m e t r l c a l l y

as s i l v e r c h l o r i d e . Nitrogen was determined by K j e l d a h l ' s method.

Conductance was measured on a c o n d u c t i v i t y b r i d g e (Elode1 No. L370873,

Cambridge Instruments , U.L) a t 10-3M c o n c e n t r a t i o n . I n f r a r e d

spectra were recorded on a Perk in Elmer 621 ins t ruments as Nujol m u l l s

o r n e a t i n t h e range of 4000-200 cm" u s i n g a C s I window.

2 P r e p a r a t i o n of B-ketoamines

p-Ketoamines were synthes ized by adding a 50% mole excees of t h e

a p p r o p r i a t e primary amines d i r e c t l y t o p -ketoamines. The reaction

mixture w a s hea ted a t 100°C for - 5 h r i n t h e presence of c a l c i u m

s u l p h a t e and t h e product were p u r i f i e d by vacuum d i s t i l l a t i o n .

2

I

General p r e p a r a t i o n of 182 adducts of a r s e n i c and antimony t r i c h l o r i d e w i t h 13-ketoamines (Table 1)

To a s t i r r e d s o l u t i o n of a r s e n i c t r i c h l o r i d e (0.36 g ; 2 -1) i n I

benzene ( -15 mL) o r a n t i m n y t r i c h l o r i d e (0.46 g: 2 nnnol ) , i n

benzene ( -15 mL)

w a s added,dropwise a t -15OC. S t i r r i n g w a s cont inued f o r 4 h r . The

s e p a r a t e d s o l i d was f i l t e r e d and washed with benzene, d r i e d a t

3OoC/0.1 nun f o r 5 hr .

thep-ke toandne ( 4 k l ) i n benzene ( -50 mt)

- P r e p a r a t i o n of I t 1 a d d u c t s of a n t l m n y p e n t a c h l o r i d e w i t h /3 -ketoandnes (Table 1)

Antimony p e n t a c h l o r i d e (0.6 g: 2 m1) i n ch loroform ( - 2 0 I&), was

added dropwise to a s o l u t i o n of t h e p-ke toamine ( 2 numl) i n c h l o r o f o r n

( -30 nu,) w i t h c o n s t a n t s t i r r i n g . The s t i r r i n g w a s cont inued f o r 8 h r .

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ADDU(TIS OF ARSENIC AND ANTIMONY TRlCHLORIDES

An inso luble oi ly product was seperated ou t by decantat ion. I t was

washed with chloroform and f i n a l l y d r i e d i n vacuo a t 3O0c/O.i mn

€or 5 hr .

1033

RESULTS AUD Mscu8sTotJ

The adducts of arsenic and antiimny t r i c h l o r i d e erd ant invny

pentachlor ide with f3-katoamfnes were prepared by t h e fol lowing

reaction.

MC1 + 2R’COCHC (NHR) Me + Mc1 3. 2R ‘COMC (NHR) Me

sbC15 + MeCOCHC(NHR)Me _j SbC15.MBCCCHC(NHR)Me

(H P AS, Sbt R’ sz Me? R = Me, E t , i-Pr)

Adducts of arsenic t r i c h l o r i d e with MeCCCHC(NHMe) Me are c r y s t a l l i n e

s o l i d s and w i t h MecoCl‘iC(NHR)Me (R - B t , i -Pr) are l i g h t yellow viscous

l i q u i d s (Table 1). The a d d i t i o n compounds af antimny t r i c h l o r i d e

and p e n t a c h l o d d e with HecOCHc(NtiR) Me are yellow viscous l i q u i d s

whereas antimony t d d h l o r i d e adducts with PhCoCHC(NHR)Me are so l id .

A l l t h e s e adducts are i n s o l u b l e i n commn non-polar solvents but

are s o l u b l e i n accetonitrile. The molar conauctance v a l u e s of t h e

adducts of arsenic t r i c k l o r i d e with /3 -kctoantines i n a c e t o n i t r i l e do

n o t correspond completely t o l r l e l e c t r o l y t e s . The lower values

i n d i c a t e t h a t t h e r e is an equi l ibr ium i n so lu t ion , perhaps of the

fol lowing type . 5

AsC13.2ikCGCiiC(~R) tk ,- [AsCla.MeCGCHC(NHR) Me(CH3CN)] +Cl’

I n f r a r e d spectral d a t a (Table 2) are very h e l p f u l i n ceter-

ming t h e mode of bonding o f p-ketoamines t o metal i o n s i n t h e i r

adducts. I n t h e i n f r a r e d spectra of t h e arsenic t r i c h l o r i d e adaucts

t h e observed bands i n the region 3450-3200 cm” are due to Z)(OH) or

I)(=) vibration nodes. The complete absence of bands above 1605 c m - l

i t l d i c a t e s t h e bonding i n t e r a c t i o n of t h e ketonic oxygen with A s ( I I 1 ) .

The two very i n t e n s e bands in t h e region 1605-1540 cm” are assignable

t o 3 ( O - C ) and 3(C=N) vibra t ion , respec t ive ly . The coordinat ion

through carbonyl oxygen is f u r t h e r subs tan t ia ted by t h e presence of a

s t r o n g band a t 58822 cm” ass ignable t o the

6

7 AS-0) vibra t ion .

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Tabl

e 1.

Physical Data of the C

ompl

exes

- 8

P

No.

Compounds

Found

CCalcd.)

% .h at 25OC

Yield

M.P.

(OC

) Colour/Nature

( %I

Metals

c1

N (c =

1 x

IO-~M)

1.

AsC13.2MeCOCHC(NHMe)Me

18.39

25.67

7.00

55

(18.89) (26.16) (6.87)

CC12H22C1302N2A3

95

154-56'

Col

ourl

ess

soli

d

2. AsC13.2MeCOCHC(NHEt)Me

17.35

24.55

6.40

32

95

- Light yellow viscous

(17.20) (24.44) (6.42

[! 1 4H2 4c1 3O 2N2AS1

3. AsC13.2MeCOCI.IC(NHi-Pn),Me. 16.94

22.82

6.05

.43

96

- Li

ght ye

llow

viscous

Cc 16H 30c1 3' zN2*q

(16.49) (22.99)

(6.08)

4. SbC13.2MeCOCHC(NHMe)Me

27.39

23.60

6.27

89

95

- Li

ght yellow viscous

(27.10) (23.40)

(6.16)

rc 12H22Cl30 2N2Sb7

5. SbC13.2MeCOCHC(NHEt)Me

24.88

24.03

5.72

108

94

- Li

ght yellow viscous

rc 1dH2 4c130 zN

2sq

(24.80) (24.15) (5.61)

- Li

ght yellow viscous

z 80

95

I 6.

SbC13.2MeCOCHC(NHi-Pr)Me

23.54

20.75

5.45

(23.84) (20.88) (5.47)

[c&oc130~N2sbl

z !$ 3

7.

SbC13.2yhCOCHC(NA14e)Me

21.00

18.41

4.91

10 9

95

150d

Ligh

t br

own

soli

d

>

z U z

(21.05) (18.43) (4.84)

Lc 22H26C1302N2Sbl

- Contd..

.e

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Tab

le

1.

(Co

ntd

.)

> 5

- R

No.

Co

mpou

nds

Fo

un

d(C

a1cd

.)

"x

Am

at 2

SoC

Y

ield

M.P.

(Oc)

C

bl,

ou

r/ri

atu

re

(%I

Metals

C1

N

(C

= 1

x

10-3

M

8.

9.

10.

11.

12

.

92

96

1

70

d

Co

lou

rle

ss s

oli

d

n

Lic

:Cip

30C

1302

N2S

bJ

Cc2

fi34

cl30

2NzS

b 7

1

SbCl 3.

2Ph

CO

CH

C (

NH

E t) Me

20.3

0 17

.69

4.57

(2

0.0

7)

(17.

50)

(4.6

2)

SbC

13.2

PhC

OB

E (N

nl-P

r) Me

19.4

5 16

.51

4.38

8

6

95

1

95

d

Co

lou

rles

s s

oli

d

(19

.29

) (1

6.79

) (4

.41)

SbC15.MeCOCEfC(NHMe) Me

28.8

7 4

3-0

3

4.00

1

44

(2

8.9

0)

(42.

96) (3.93)

tc6x

11c1

5O

NSb

1

Yellow viscous l

iqu

id

~ 98

-

Ye

llo

w v

lsc

ou

s li

qu

id

Sb

cl

.Mec

ocH

c (M

iE t) Me

29.0

2 41

.50

3.85

10 3

97

-

(29

.00

) (4

1.54

) (3

.80)

c

c+

1rp

50

Na

sbC

15

.WO

WC

(Nti

i-P

r)M

e 26

.92

39.6

2 3

-50

12

9

8

- Y

ello

w v

isco

us

liq

uid

@

sH15

Cl

50NSb]

(27.

05)

(40.

03)

(3.4

8)

~

Am =

bla

r c

on

du

ctan

ce (

cm2

ohm

'' m

ole-

') of

10

'3M

so

luti

on

in

a

ce

ton

itri

le.

d

= de

com

pose

d

a V

alu

es i

n p

are

nth

ese

s c

orr

esp

on

d t

o t

he

th

eo

reti

ca

l v

alu

es.

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Tab

le

2.

Imp

ort

an

t I

R B

ands

(c

m'l)

of A

dd

uct

s of

Ars

enic

Tri

ch

lori

de

, A

ntim

ony

'rri

ch

lori

de

an

d A

ntim

ony

Pe

nta

ch

lori

de

wit

h p

- Ket

oam

ines

1.

2.

3.

4.

5.

6.

7.

8. 9.

10.

11.

12.

AsC

l 3. 2

MeC

OCH

C (N

HM

e) M

e A

sCl 3

. 2M

eCO

CHC

(NH

Et)

Me

AsC

l 3. 2

MeC

OC

Hc

"Hi-

Pr)

Me

Sb

cl 3

. 2M

eCO

CHC

(NH

h) M

e Sb

C13

.2M

eCO

CH

C(N

HE

t) M

e sb

cl 3

. 2M

eCO

CHC

(Mi-

Pr)

M

Sb

cl 3

. 2P

hCO

CH

C (N

HM

e) M

e S

bcl

3. 2

PhC

OC

LiC

(NIB

t) Me

Sbcl 3.

2PhC

OC

HC

(N

Hi-

Pr)

Me

Sbcl

5.M

eC0C

HC

(N

HM

e) Me

Sbc1

5.M

eCO

CH

C(N

HE

t) Me

Sbcl

.MeC

OCH

C (N

Hi -

Pr)

he

3 450

-320

0 b

34

50-3

200b

34

50-3

2001

3

3400

-300

0b

3400

-300

033

3 400

- 3000

b 34

00-3

1003

3 34

00-3

1503

3 34

00-3

100b

34

00-3

OO

Ob

3400

-300

0b

3 400

- 30

00 b

- - 1

70

0s

1700s

16

90

s 1

69

1s

17

00

s 1

69

8s

17

00

s 1

69

9s

16

92

s

16

02

s 1

60

5s

16

03

s

15

90

s 1

58

6s

15

90

s 1

58

9s

15

86

s 1

5 90

s

15

87

s 1

59

0s

1588s

15

40

s 1

54

5s

15

42

s 1

45

0s

14

40

s

14

50

s 1

45

9s

14

65

s 1

45

0s

14

62

s 1

46

0s

14

63

s

56

0s

56

2s

57

0s

58

9s

56

1s

57

8s

57

2s

. 5

80

s 57

3s

59

0s

58

6s

58

8s

36

0s,

330

w

359s

, 33

2w

310b

32

2s.

300w

31

2s,

280

w

313w

, 30

lw

3

12

s, 2

80w

3

10

s, 2

32w

32

0s.

290w

340s,

312w

33

26

,31

2~

r *

z c)

X

SW

-tra

wer

e re

cord

ed a

s N

ujo

l fi

lm i

n t

he

ran

Qe of 4

000-

200

cm-'

ex

ce

pt

Sl.

No.

10,

11 a

nd

12

9

z U

whi

ch w

ere

reco

rded

as

liq

uid

fil

m.S

pe

ctr

a

of

the

S1. No.7,

8 a

nd

9 w

ere

rec

ord

ed

a

s K

Br P

ille

ts.

b.

bro

ad:

s, st

rong

; w,

w

eak.

M

=

AS

, sb

.

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ADDUCTS OF ARSENIC AND ANTIMONY TRICHLONDES

I n t h e far- infrared region (360-330 cm") t h e observed bands a t

3592 1 and 33121 are due t o (As-C1) s t reching v ibra t ions .

1037

I n t h e absence of s t r u c t u r a l evidence of s i m i l a r types of

a r s e n i c t r i c h l o r i e e adducts w e cannot propose t h e f i n a l conf igura t ion '

of t h e a r s e n i c t r i c h l o r i d e a d d x t s with p-ketoamines. On t h e basis

of the n e a r e s t known s t r u c t u r e of s i m i l a r types of 112 adducts of

antimony t r i c h l o r i d e with lJh3p0, Ph3As0 and D N O 9 , a square

pyramidal s t r u c t u r e could be propused for t h e covalen t form 02

AsC13. 2E€ea?CHC(NHfi) M e (Fig. l)..The oxygen atoms of t h e t w o P-ketoamines

mieties may be i n a l i n e a r arrangement and one of t h e c h l o r i n e atoms

of a r s e n i c t r i c h l o r i d e may adapt t h e trans p o s i t i o n i n comparision t o

t h e lone p a i r of e l e c t r o n s .

8

-

The sdducts of antimony t r ichlor ic?e and antimony pentachlor ide

with p-ketoamines a r e It1 e l e c t r o l y t e s and t h e n a t u r e o f t h e

ionic Species are CSbC12.2R'COCHC(~JHR)Me(~3CN)]+C1- or

[SbC14.MeCOCHC(NHR)Me(B13CM)) +Cl-,

a n t i m n y t r i c h l o r i d e and pentachlor ide with p-ketoamines t h e

r e l e v a n t i n f r a r e d bands have been tabula ted (Table 2 ) . The weak

broad bands i r . t h e high frequency region 3400-3000 cm" are

due t o 1)(on) or $(hall v i b r a t i o n modes. I n c o n t r a s t to arsenic

t r i c h l o r i d e adducts, a l l the adducts o f antimony t r i c h l o r i d e

and pentachlor ide with p-ketoamines d isp lay a n i n t e n s e band

i n t h e region 1700-1690 c d l due t o t h e 3(c=O) v ibra t ion .

T h i s is c o n s i s t e n t with t h e f a c t t h a t coordinat ion to antimony

t a k e s p lace through t h e n i t rogen a t o m of t h e azomethine gtoup

( k N ) . The absorpt ion band in the region 1592-1585 c m - l is

due to t h e 3(C---C) v ibra t ion . The band due t o t h e 3(C=N)

v i b r a t i o n is observed i n t h e range o f 1463-1440 cm".

respect ively. For t h e adducts of

The presence o f a new absorpt ion band i n t h e fa r - inf ra red

(580-560 cm") i n a l l t h e adducts is due to the

vibra t ion . The appearance of only 3(Sb-N) v i b r a t i o n bands

also supports t h e bonding i n t e r a c t i o n of t h e p-ketoamine t o

r)(Sb-N)

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1038 SINGH AND PANDEY

C l I O

Fig. 1. Square Pyramidal structure for ArCl3-2MeCOCHC (NMR) Me

Ct

Fig. 2. Square pyramidal structure for SbClj*2MeCOCHC (NHR) Mu

Cl

Cl. C l 1 ct

Fig. 3. Octahudral structure for Sb CIS- MU COCHC ( NHR) MU

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ADDUCTS OF ARSENIC AND ANTIMONY TRICHLORlDES 1039

S b ( I I 1 and V) through t h e n i t rogen atom. I n both antimony

t r i c h l o r i a e and pentachlor i 3e adducts , t h o bands due t o d(Sb-Cl)

b i b r a t i o n modes were observed in t h e region 340-280 cm-'. On

t h e Oasis o f t h e known structure of t h e l r 2 acecc t of

9

antimony t r i c h l o r i d e w i t i ? an i l ine" ans ~ - b u t y r o l a c t a m ~ ' t h e

s t ructure (Fig. 2) for SX13.2R'COCHC(EHR)Me i n t h e s o l i d state with a

s te reochemica l ly ac t ive lone -pair of e l e c t r o n s occupying t h e

s i x t h m s i t i o n is suggested.

The s te reochemis t ry of l a 1 adducts of antimony pentachlor i se

with p-ketoamine, SbC15.MeCOCH (1HR) Me, can be considered to possess

an o c t a h e d r a l . s t r u c t u r e (Fig. 3).

The a u t h o r s a r e thankful to t h e a u t h o r i t i e s of Banaras Hindu

Univers i ty for providing f a c i l i t i e s . The a u t h o r s also wish

to e x p r e s s t h e i r g re te fu lnesa to CSIR, N e w Delhi, f o r f i n a n c i a l

assistance.

1. T.M. -Hssu, D.F. Martin and T. meller, Inorq. Chem., 2, 287 (1963).

2.

3. D.H. Gerlach and R.H. Holm, J. Am. Chem. SOC., 90, 4184 (1968).

4. A.I. Vogel, "A Text Book of Quan t i t a t ive Inorganic Analysisg1,

G.W. Everett and R.H. Holm, Inorg. Chem., 1, 716 (1968).

Longmans, Lcndon, P. 392, 1978.

5. J.c. Summers arf H.H. Silver, Inorg. Chem., 9, 862 (1970).

6. R.P. s ingh and V.D. Gupta, Spectrochim. A c t a . s. 407 (1984).

7 .

8. L. Golic and S. Milicov, Acta Crystal logr . , 3379 (1978).

9. R.P. O e r e t e l , Spectrochim. A c t a . 659 (1970).

10. R. Hulme and D. Uu l l en and J.C. Scru t ton , Acta Crystal logr . ,

J.Kaufmann and F. Fober, J. Organomet. Chem. ,8 l , 59 (1974).

- 25, 171 (1969) . 11. S.T. Yuan and S.K. Maaan, Inorganica Chim. Acta, u), 463 (1972).

Received: 29 October 1990 Referee I : L . K . Krannich Accepted: 23 April 1992 Referee 11: L. D . Freedman

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