Synthesis and reactions of sterically hindered α-naphthyl- and cyclohexylantimony(V) derivatives

Article abstract of DOI:10.1081/SIM-120003215

Interhalogen and halo-pseudohalogens IX (X=Cl, Br, N₃, NCO), (SCN)₂, S and TeCl₄ add oxidatively to (α-C₁₀H₇)₃Sb to afford (α-C₁₀H₇)₃SbIX, (α-C₁₀

Full text of DOI:10.1081/SIM-120003215

Synthesis and Reactivity in Inorganic and Metal-Organic
Chemistry
ISSN: 0094-5714 (Print) 1532-2440 (Online) Journal homepage: http://www.tandfonline.com/loi/lsrt19
Synthesis And Reactions Of Sterically Hindered α-
Naphthyl- And Cyclohexylantimony(V) Derivatives
Santosh Agnihotri , Prem Raj & Kiran Singhal
To cite this article: Santosh Agnihotri , Prem Raj & Kiran Singhal (2002) Synthesis And
Reactions Of Sterically Hindered α-Naphthyl- And Cyclohexylantimony(V) Derivatives, Synthesis
and Reactivity in Inorganic and Metal-Organic Chemistry, 32:2, 399-417, DOI: 10.1081/
SIM-120003215
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Date: 21 December 2016, At: 20:34

SYNTH. REACT. INORG. MET.-ORG. CHEM., 32(2), 399–417 (2002)
SYNTHESIS AND REACTIONS
OF STERICALLY HINDERED
a-NAPHTHYL- AND
CYCLOHEXYLANTIMONY(V)
DERIVATIVES
Santosh Agnihotri, Prem Raj,* and Kiran Singhal
Department of Chemistry, Lucknow University,
Lucknow-226 007, India
ABSTRACT
Interhalogen and halo-pseudohalogens IX (X ¼ Cl, Br, N3,
NCO), (SCN)2, S and TeCl4 add oxidatively to (a-C10H7)3Sb
to afford (a-C10H7)3SbIX, (a-C10H7)3Sb(SCN)2, (a-C10H7)3
SbS and (a-C10H7)3SbCl2, respectively. Reactions of R3SbCl2
(R ¼ a-C10H7, cyclo-C6H11) with MY (M ¼ Ag, K, Na; Y ¼
SCN, CN, NCO, N3) yielded the penta-coordinate products,
R3Sb(SCN)2, R3Sb(NCO)2, (a-C10H7)3Sb(CN)2 and (a-C10
H7)3Sb(N3)2. The compounds (a-C10H7)3SbIN3, (a-C10 H7)3
SbI(NCO), (a-C10H7)3SbI(SCN) and (a-C10H7)3SbI(SeCN)
are also accessible by selective replacement reactions of (a-
C10H7)3SbIClor ( a-C10H7)3SbIBr with the corresponding
metalsalts. Hydrolysis of R 3SbCl2(R ¼ a-C10H7, cyclo-C6H11)
afforded (R3SbCl)2O-type compounds. (a-C10H7)3Sb inserts
*Corresponding author. E-mail: premraj01@indiatimes.com
399
Copyright # 2002 by MarcelDekker, Inc.
www.dekker.com

400
AGNIHOTRI, RAJ, AND SINGHAL
into the N-chloro bond of N-chlorosuccinimide and N-cho-
lorophthalimide to give (a-C10H7)3Sb(Cl)NCO(CH2)2CO and
(a-C10H7)3Sb(Cl)NCO(C6H4)CO. These haloimides may also
be prepared by the interaction of (a-C10H7)3SbCl2 with the
corresponding sodium salt of the imido moiety.
INTRODUCTION
Despite a voluminous amount of work done on the chemistry of organic
derivatives of antimony(III) and antimony(V), those having sterically larger
moieties viz., naphthyl, cyclohexyl and mesityl groups, bound to antimony,
have been studied to a very limited extent only175. Except for preliminary
reports on the synthesis of triorganoantimony(V) dihalides5,6, R3SbX2
(R ¼ a-C10H7, cyclo-C6H11; X ¼ Cl, Br) and tri(cyclohexyl)antimony(V)
dicarboxylates7, no published data on the synthetic and reactivity aspects of
such compound are available in the literature, In sharp contrast, the corre-
sponding derivatives of Group 14 metals (M ¼ Sn, Pb) are welldocumented8,9
.
The main objective of this work was to explore the effect of bulky a-
naphthyland cyclohexylgroups bound to antimony in its þ3 and þ5 oxida-
tion states in context of their preparation, stability and chemical behaviour.
This is even more important in light of the fact that significant changes in
geometry and other physico-chemicalaspects have been observed eariler on
changing the nature and contents of organic groups bound to antimony1.
The present communication deals with:
(i) Oxidative addition reactions of (a-C10H7)3Sb with interhalogens,
halo-pseudohalogens, pseudohalogens, elemental sulphur and
tellurium tetrachloride.
(ii) Metathetical
and
selective
replacement reaction
of
R3SbCl2(R ¼ a-C10H7, and cyclo-C6H11, and (a-C10H7)3SbICl)
with the appropriate metalsatls to give disubstituted pseudo-
halides and mixed halo-pseudohalides.
(iii) Insertion reactions of (a-C10H7)3Sb into N-halogen bonds.
RESULTS AND DISCUSSION
OxidativeAdditions
Both ICI and IBr react with tri(a-naphthyl)antimony to give the
respective oxidative addition products.

a-NAPHTHYL- AND CYCLOHEXYLANTIMONY(V)
401
0ꢀC
ða-C10H7Þ3Sb þ IX ðX¼ÀC!l; BrÞða-C10H7Þ3SbIX
ð1Þ
Similarly, freshly generated solutions of (SCN)2, IN3 and I(NCO) in
CCl4 or CH3CN add oxidatively to (a-C10H7)3Sb to produce the compounds
(a-C10H7)3Sb(SCN)2, (a-C10H7)3SbIN3 and (a-C10H7)3SbI(NCO), respec-
tively. Details of the experimental and analytical data are recorded in Table I.
ða-C10H7Þ3Sb ÀÀÀÀÀ! ða-C10H7Þ3SbIX
ð2Þ
CCl4ðÀ10ꢀCÞ
ðX ¼ N3; NCOÞ
ðSCNÞ2
ða-C10H7Þ3Sb ÀÀÀÀÀÀÀÀÀÀÀ! ða-C10H7Þ3SbðSCNÞ2
CCl4ðÀ5ꢀ to À10ꢀCÞ
ð3Þ
The reaction with (SCN)2 was invariably performed in the dark to
prevent its polymerisation. (cyclo-C6H11)3Sb was also found to undergo
oxidative addition reaction with (SCN)2 to give (cyclo-C6H11)3Sb(SCN)2 (9).
TeCl4 also adds oxidatively to R3Sb at room temperature in acetonitrile-
ether solvent mixture to yield R3SbCl2 (R ¼ a-C10H7, cyclo-C6H11) in
moderate yield. TeCl4 is reduced to blackish-grey elemental tellurium which
is easily filtered off. Elemental sulphur adds oxidatively to (a-C10H7)3Sb in a
dry nitrogen atmosphere to give (a-C10H7)3SbS (6). Similar observation
have been made for triarylantimony(III) compounds10. (a-C10H7)3SbS (6)
was also obtained by passing H2S gas into an ethanolic ammonia solution of
(a-C10H7)3SbCl2.
ða-C10H7Þ3Sb þ S EÀtÀOÀHÀ=ÀN!H3ða-C10H7Þ3SbS
ð4Þ
Metathetical Reactions
The treatment of R3SbCl2(R ¼ a-C10H7, cyclo-C6H11) with the corre-
sponding metalsatls in methanol =benzene leads to the formation of di-
substituted antimony(V) derivatives.
MeOH=C6H6
R3SbCl2 þ 2MY ÀÀÀÀÀÀÀ! R3SbY2 þ 2MCl
ð5Þ
ðM ¼ Na; K; Ag; Y ¼ NCS; N3; NCO; R ¼ a-C10H7; cyclo-C6H11Þ

402
AGNIHOTRI, RAJ, AND SINGHAL

a-NAPHTHYL- AND CYCLOHEXYLANTIMONY(V)
403

404
AGNIHOTRI, RAJ, AND SINGHAL
Selective Replacement Reactions
Reactions involving equimolar amount of mixed iodohalo compounds
R3SbIX (X ¼ Cl, Br) and metal salts of pseudohalides yielded mixed
iodopseudohalo derivatives through exclusive replacement of chloride or
bromide by a pseudohalo group. Interestingly, the iodide invariably remains
bonded to the metal, irrespective of the nature of the metal salt used.
ða-C10H7Þ3SbICl þ NaN3À! ð a-C10H7Þ3SbIN3 þ NaCl
ð6Þ
ð7Þ
ða-C10H7Þ3SbIBr þ AgY ÀÀÀÀÀÀ! ð a-C10H7Þ3SbIY þ AgBr
ðY ¼ NCO; NCS; SeCNÞ
This behaviour of organoantimony compounds is somewhat different
from what is observed for similar reaction of diaryltin and lead mixed
halides where both of the different halo groups are replaced by anionic
groups11,12. It may be noted that in case of Group 14 metals, identically
placed iodine is more readily replaced by silver salts and the chloride and
bromide are replaced by the anions attached to alkali metals. Selective
replacement reactions of halo groups have been reported earlier in case of
antimony and tellurium derivatives14716. The products (a-C10H7)3SbIN3 (3),
(a-C10H7)3SbI(NCO) (4), (a-C10H7)3SbI(SCN) (8) and (a-C10H7)3SbI-
(SeCN) (14) obtained through exclusive replacement of bromo or chloro
groups [Eqs. (6) and (7)] are similar to those obtained by the oxidative
method [Eqs. (2) and (3)] described above. The compound (a-C10H7)3-
SbIN3 obtained by the two different routes [Eqs. (2) and (6)] have similar
melting points and superimposable IR spectra. Similarly, the compound
(a-C10H7)3SbINCO prepared via Eqs. (2) and (7) were found to be identical.
Hydrolysis and Quaternizations
The hydrolysis of alkaline ethanolic solutions of R3SbCl2 proceeded to
give the binuclear, oxobridged compounds (a-C10H7)3ClSb-O-SbCl(a-
C10H7)3 (15) and (cyclo-C6H11)3ClSb-O-SbCl(cyclo-C6H11)3 (16).
ClCl
j
j
Hydrolysis
R3SbCl2 ÀÀÀÀÀ!
R Sb-O-SbR
3
ð8Þ
3
ðR ¼ a-C10H7; cyclo-C6H11Þ

a-NAPHTHYL- AND CYCLOHEXYLANTIMONY(V)
405
Attempts to obtain (a-C10H7)3SbBr by the interaction of (a-C10H7)3Sb
with a-C10H7Br in the presence of anhydrous AlCl3 was not successful, even at
high temperature (140 ꢀC). The failure of the reaction may partly be ascribed
to the bulky nature of the naphthyl moiety which hinders the formation of the
desired product. However, such quarternary products are readily obtained in
case of relatively smaller organic groups in R4SbX where R ¼ alkyl and aryl.
Insertion Reactions
N-Chlorosuccinimide and N-chlorophthalimide readily interact with
tri(a-naphthyl)antimony to provide insertion products by the equations
shown below:
−
°C
(α
(α-C10H7)3Sb+ ClNCO(CH2)2CO
(α-C10H7)3Sb+ ClNCO(C6H4)CO
NCO(CH2)2CO
ð9Þ
−
°C
(α
NCO(C6H4)CO
ð10Þ
(α-C H ) Sb(Cl)
NCO(C6H4)2CO (18)
(α-C10H7)3Sb(Cl)NCO(CH2)2CO (17) and
10
7 3
could also be obtained by the 1:1 molar ratio reaction of
(a-C10H7)3SbCl2 with the corresponding sodium salt of the imide moiety.
reflux
(α
(α-C10H7)3SbCl2+ NaNCO(CH2)2CO
NCO(CH2)2CO
ð11Þ
Attempts to replace both halo groups employing an excess ( > 2 mole)
of sodium salt of the imide was not successful and this can be ascribed to the
bulky nature of the amido=imido group as well as the naphthyl group. In
sharp contrast to this, disubstituted organoantimony(V) amides, R3Sb-
(NR2)2 (R ¼ C6H5, C6F5, p-CH3C6H4), were readily obtained14,15
.

406
AGNIHOTRI, RAJ, AND SINGHAL
The observed molecular weight data of these compounds in freezing
benzene were found comparable with those of the theoretical values which
suggests that the compounds exist as monomers. The molar conductance
values of 10À3 M solutions in acetonitrile of the newly synthesised deriva-
tives range between 13735 ohmÀ1 molÀ1 cm2, which shows their non-con-
ducting nature17. These compounds are stable at room temperature and
moderately soluble in organic solvents.
Infrared Spectra
IR absorptions corresponding to a-naphthylgroups bound to anti-
mony are in close conformity with the reported values of analogous tri(a-
naphthyl)antimony. They are comparable with those of similar organotin
compounds18. The diagnostic IR absorption bands due to pseudohalo
groups have been identified and are listed in Table II.
Tri(a-naphthyl)antimony Iodide Azide (3)
A strong band at 2050 cmÀ1 corresponds to the asymmetric vibration
while the symmetric stretching frequency was located at 1250 cmÀ1 as a
medium-intensity band. A very weak-intensity band appearing at 670 cmÀ1
may be assigned to the bending mode. The position of these bands is nearly
the same as reported for covalently bonded Group 14 and 15 organometal
azides19721
.
Tri(a-naphthyl)antimony Iodide Isocyanate (4)
Compared to phenylanaolgs, the asymmetric stretching mode is
observed at a lower frequency, at ꢁ 2000 cmÀ1, but is consistent with the iso
structure of the cyanate group22,23. The other absorption band of medium
intensity at ꢁ 1370 cmÀ1 is due to the symmetric stretching mode. The
absorptions associated with the -NCO bending mode appear at ꢁ 640 cmÀ1
as a band of medium to weak intensity.
Tri(a-naphthyl)antimony Dithiocyanate (5)
A very strong and broad band due to asymmetric stretching (-NCS) in
the 199072005 cmÀ1 range suggests the bonding to be iso, i.e., nitrogen

a-NAPHTHYL- AND CYCLOHEXYLANTIMONY(V)
407

408
AGNIHOTRI, RAJ, AND SINGHAL
bonded. Other important features in favour of a nitrogen linkage are the
appearance of the C-S symmetric stretching of very weak intensity at
1055 cmÀ1 and a strong band due to d(NCS) bending is observed at
472 cmÀ1. These modes of vibration favour an iso structure24.
Tri(a-naphthyl)antimony Dicyanide (8)
The organic isonitriles R-NC absorb at a lower frequency at
216072120 cmÀ1 than the nitriles25727 R-CN (226072220 cmÀ1). No other
frequency of diagnostic value, except the one at 1995 cmÀ1 for the CꢂN
group, could be located. A comparison with the previous work thus indi-
cates the presence of a nitrogen-bonded cyanide moiety28732
.
Tri(a-naphthyl)antimony Iodide Selenocyanate (14)
In the present investigation, where the organic moiety is a bulky group
i.e., a-naphthyl, the position of nsym(C¼N) is lowered i.e., at 2000 cmÀ1 as a
very strong peak compared to the phenylanalogs, but is consistent with a N-
bonded -NCSe group. In addition to this, an absorption of medium intensity
at 590 cmÀ1 also supports the iso structure of the newly synthesised
compound33,34. The deformation mode d(NCSe) was tentatively assigned at
490 cmÀ1. The Sb-N band in the selenocyanate derivative has been assigned
at 360 cmÀ1
.
m-Oxybis[(a-naphthyl)antimony Chloride] (15)
In this compound an additionalsharp band at ꢁ 705ꢃ5 cmÀ1 was
observed which can be assigned to the Sb-O-Sb vibration35,36 indicating the
formation of an oxo-bridged binuclear derivative.
Tri(a-naphthyl)antimony Chloride Succinimide (21)
This compound displays a strong band due to nas(CO) at 1700 cmÀ1
assignable to an ‘‘ester-like’’ CO group. The symmetric stretching mode is
observed at 1327 cmÀ1. Pattern and position of the bands are comparable
with those of known amide derivatives37.

a-NAPHTHYL- AND CYCLOHEXYLANTIMONY(V)
409
1H NMR Spectra
The proton magnetic resonance spectra of a representative compound,
tri(a-naphthyl)antimony chlorosuccinimide, in CDCl3 at room temperature
showed a multiplet centred at d 8.5677.50 ppm for a-C10H7 protons and a
singlet at d 2.35 ppm for (-COCH2-)2 protons. The integration of the peak is
consistent with the proposed formulation of the compounds.
On the basis of IR, and 1H NMR evidence coupled with their monomeric
and non-conducting nature and in accordance with the structure of other
organoantimony(V) compounds19,35,36,37, the newly synthesized derivatives
are assigned to have a trigonalbipyramidalstructure as shown in Fig. 1.
EXPERIMENTAL
Materials and Methods
Tri (a-naphthyl)antimony5 was prepared from a-naphthylmagnesium
bromide, a-C10H7MgBr, and anhydrous antimony trichloride (Fluka) and
was converted to the corresponding dihalides by the reported method5.
Tri(cyclohexyl)antimony dichloride3,4 was synthesized by known methods.
Iodine monochloride (Fluka) was used as such. Iodine monobromide was
prepared and purified by the reported method38. Freshly prepared iodine
isocyanate39, iodine azide40 and thiocyanogen41 in approximately known
concentration were generated in an appropriate solvent by standard meth-
ods. Except for NaN3, the freshly prepared metal salts were dried in vacuo
before use (NaN3 of Fluka was used as such. Direct heating of NaN3 was
avoided to prevent any explosion). All solvents were purified and dried by
standard procedures and reactions were carried out in a dry nitrogen
atmosphere. IR spectra were recorded in the range 40007200 cmÀ1 in KBr
or CsI pellets on a Perkin-Elmer 577 spectrophotometer. The molar
conductance of 10À3 M solutions was determined at 25 ꢀC with a PR-9500
Phillips conductivity assembly. Molecular weights were determined
cryoscopically in benzene using a Beckmann thermometer of ꢃ0.01 ꢀC
accuracy.
Preparation of the Antimony(V) Derivatives
Details of the typical experiments are described below. Relevant IR
assignments, analytical data and molar conductance values are listed in
Tables I and II.

410
AGNIHOTRI, RAJ, AND SINGHAL
Figure 1. Suggested structures of the complexes.
Reaction of (a-C10H7)3Sb with ICland IBr ( 1) and (2)
A solution of iodine monochloride (0.325 g, 2 mmol) in carbon tetra-
chloride (20 mL) was added dropwise to a stirred solution of tri(a-naph-
thyl)antimony (1.0 g, 2 mmol) in the same solvent (40 mL) at 0 ꢀC during 1 h.
The reactants were allowed to attain room temperature and stirred further
for half an hour to ensure complete reaction. Concentration of the solution
followed by the addition of petroleum ether (60780ꢀ) afforded a dark yellow
crystalline solid, tri(a-naphthyl)antimony(V) chloride-iodide (1); yield
0.914 g.

a-NAPHTHYL- AND CYCLOHEXYLANTIMONY(V)
411
Similarly, the 1:1 molar reaction of tri(a-naphthyl)antimony (1.004 g,
2 mmol) and iodine monobromide (0.414 g, 2 mmol) yielded tri(a-naphthyl)-
antimony(V) bromide iodide (2); yield 1.006 g.
Reaction of (a-C10H7)3Sb with IN3 and I(NCO) (3) and (4)
A freshly generated solution of iodine azide (0.169 g, 1 mmol) in acet-
onitrile (20 mL) was added to a vigorously stirred solution of tri(a-naph-
thyl)antimony (0.502 g, 1 mmol) in the same solvent (30 mL) at À10 ꢀC during
half an hour. The reactants were stirred for 1 h at the initial temperature and
then allowed to come to room temperature. The solution was then evapo-
rated under reduced pressure and cooled overnight after adding petroleum
ether (60780ꢀ) to afford a mustard coloured crystalline solid which was
identified as tri(a-naphthyl)antimony azide iodide (3); yield, 0.376 g.
(a-C10H7)3SbINCO (4) was obtained similarly as a white crystalline
solid by the method described above using an equimolar ratio of corre-
sponding reactants; yield, 0.342 g.
Reaction of (a-C10H7)3Sb with (SCN)2 (5)
A freshly prepared solution of thiocyanogen (0.116 g, 1 mmol) in
CCl4 (30 mL) was added to a stirred solution (30 mL) of tri(a-naphthy-
l)antimony (0.502 g, 1 mmol) in CCl4 at À5 ꢀC during 15 min. The reac-
tion mixture was further stirred for 1 h and allowed to come to room
temperature. After the removalof the sovlent under reduced pressure, a
white solid was obtained. After recrystallization with petroleum ether
(40760ꢀ), it was identified as tri(a-naphthyl)antimony dithiocyanate (5);
yield, 0.402 g.
Reaction of (a-C10H7)3Sb with Sulphur (6)
A solution of tri(a-naphthyl)antimony (0.502 g, 1 mmol) in CH3CN
(30 mL) was refluxed with elemental sulphur (0.302 g, 1 mmol) for 1 h under
dry N2 atmosphere. The solution was concentrated under reduced pressure
and cooled overnight to afford a pale yellow crystalline solid. It was iden-
tified as tri(a-naphthyl)antimony sulphide (6); 0.363 g.
The same product was also prepared by passing H2S gas for ꢁ 20
minutes in an ethanolic ammonia (1:1) solution (40 mL) of tri(a-naphthyl)-
antimony dichloride (0.574 g, 1 mmol) at 40 C; yield, 0.347 g.
ꢀ

412
AGNIHOTRI, RAJ, AND SINGHAL
Preparation of Tri(a-naphthyl)antimony Dichloride (7)
Tri(a-naphthyl)antimony (0.503 g, 1 mmol) and tellurium tetrachloride
(0.269 g, 1 mmol) were stirred together for 2 h in ꢁ 50 mL acetonitrile and
refluxed for an hour. Metallic tellurium separated as a dark grey powder. It
was filtered and the solvent then distilled off under reduced pressure
affording a dirty-white solid which was identified as tri-(a-naphthyl)-anti-
mony(V) dichloride, m.p. 260 C (lit. 260 C); yield, 0.419 g.
5
ꢀ
ꢀ
Preparation of Tri(cyclohexyl)antimony Diisothiocyanate (9)
Freshly prepared dry silver thiocyanate (0.332 g, 2 mmol) and tri(cy-
clohexyl )antimony dichloride (0.440 g, 1 mmol) in (60 mL) dry benzene were
refluxed for an hour. The insoluble silver chloride was filtered and the solid
obtained on evaporation of the filtrate was recrystallized from a benze-
ne=petroleum ether (1:3) mixture; yield, 0.316 g. The compound was iden-
tified as tri(cyclohexyl)antimony diisothiocyante (9).
Tri(cyclohexyl)antimony(V) dicyanate (10) was prepared by the
interaction of tri(cyclohexyl)antimony dichloride (0. 442 g, 1 mmo1) and
silver cyanate (0.300 g, 2 mmol) in benzene; yield, 0.295 g.
Preparation of Tri(a-naphthyl)antimony Diazide (12)
Tri(a-naphthyl)antimony dichloride (0.574 g, 1 mmol) and sodium
azide (0.130 g, 2 mmol) in a mixture of dry benzene and methanol (1:1)
(50 mL) were refluxed for 7 h. After separating insoluble NaCl, the filtrate
was concentrated under vacuum. On addition of n-hexane (4 mL) white
crystals were obtained; yield, 0.326 g. The compound was identified as (a-
C10H7)3Sb(N3)2 (12).
Preparation of Tri(a-napthyl)antimony (V) Dithiocyanate (5)
Tri(a-naphthyl)antimony dithiocyanate (5) was prepared by the
reaction of tri(a-naphthyl)antimony dichloride (0.574 g, 1 mmol) with
silver thiocyanate (0.333 g, 2 mmol); yield, 0.402 g.
Tri(a-naphthyl)antimony(V) Dicyanide (8)
Tri(a-naphthyl)antimony(V) dicyanide (8) was prepared by the inter-
action of tri(a-naphthyl)antimony dichloride (0.574 g, 1 mmol) and silver
cyanide (0.270 g, 2 mmol) in dry benzene; yield, 0.30 g.

a-NAPHTHYL- AND CYCLOHEXYLANTIMONY(V)
Tri(a-naphthyl)antimony(V) Dicyanate (11)
413
Tri(a-naphthyl)antimony dicyanate (11) was prepared by the interac-
tion of tri(a-naphthyl)antimony dichloride (0.574 g, 1 mmol) and silver
cyanate (0.302 g, 2 mmol) in benzene; yield, 0.398 g.
Reaction of Tri(a-naphthyl)antimony Chloride Iodide with Silver
Thiocyanate (12)
A suspension of silver thiocyanate (0.085 g, 0.6 mmol) in benzene
(30 mL) was added to a solution of tri(a-naphthyl)antimony chloride iodide
(0.332 g, 0.5 mmol) in the same solvent (30 mL) and refluxed for 6 h. The
mixture was then filtered to remove silver chloride and unreacted silver thio-
cyanate. The filtrate was concentrated under reduced pressure to obtain an off-
ꢀ
white solid which was recrystallized from pertoleum ether (40760 C) and
identified as tri(a-naphthyl)antimony(V) iodide thiocyanate; yield, 0.234 g.
Tri(a-naphthyl)antimony(V) iodide cyanate (4) was obtained similarly by
the procedure described above using tri(a-naphthyl)antimony iodide chloride
(0.664 g, 1 mmol) and potassium cyanate (0.081 g, 1 mmol) in benzene; yield,
0.550 g. Tri(a-naphthyl)antimony(V) iodide selenocyanate (14) was obtained
by refluxing tri(a-naphthyl)antimony iodide chloride (0.664 g, 1 mmol) and
potassium seleno cyanate (0.144 g, 1 mmol) in benzene; yield, 0.550 g.
m-Oxybis[tri(a-naphthyl)antimony] Chloride (15)
m-Oxybis[tri(a-naphthyl)antimony] chloride was prepared by the
addition of a solution tri(a-naphthyl)antimony dichloride (1.15 g, 2 mmol)
in acetone (40 ml) to a solution of sodium hydroxide (0.04 g, 1 mmol) in
methanol(20 mL) After refluxing for 2 h, the mixture was fitlered and
the filtrate was concentrated until white crystals just started to separate out.
The compound was finally precipitated by adding water to the mixture. The
solid was filtered and recrystallized from chloroform=petroleum ether 1:1
(60780ꢀ). An off-white product identified as m-oxybis[tris(a-naphthyl)anti-
mony chloride] (15), was obtained; yield, 0.873 g.
Reaction of Tri(a-naphthyl)antimony with N-Chlorosuccinimide (17)
To a solution of tri(a-naphthyl)antimony (0.502 g, 1 mmol) in acet-
onitrile (100 mL) at À20 ꢀC was added N-chlorosuccinimide (0.134 g, 1 mmol)
at À5 ꢀC in half an hour. The excess solvent was distilled off to afford a solid

414
AGNIHOTRI, RAJ, AND SINGHAL
which was recrystallized from petroleum ether=methanol(3:1) and identified
as tri(a-naphthyl)antimony(V) chloro-succinimide (17); yield, 0.400 g.
Tri(a-naphthyl)antimony(V) chlorophthalimide (18) was obtained
by the same procedure using tri(a-naphthyl)antimony (0.502 g, 1 mmol)
and (0.182 g, 1 mmol) N-chlorophthalimide in acetonitrile at À20 ꢀC
which was recrystallized from petroleum ether=methanol(3:1); yield 0.520 g.
Tri(a-naphthyl)antimony (V) chlorosuccimide (17) was prepared as fol-
lows. Tri(a-naphthyl)antimony dichloride (0.574 g, 1 mmol) and the sodium salt
of N-chlorosuccinimide (0.121 g, 1 mmol) were refluxed in benzene=methanol
(3:1) ( ꢁ 8 mL) for 5 h. After removing NaCl, the filtrate was concentrated and
then 5 mL of n-hexane was added to afford a white compound which was
recrystallized from petroleum ether=chloroform (3:1); yield, 0.388 g.
ACKNOWLEDGMENTS
The authors thank the Director, RegionalSophisticated Instrumenta-
tion Centre, Lucknow, for microanalytical and spectral data and the Council
of Scientific & IndustrialResearch, New Dehl i, for financialassistance.
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Received February 24, 1994
Accepted November 30, 2001
Referee I: L. K. Krannich
Referee II: R. P. Hotz