International Journal of Scientific & Engineering Research, Volume 4, Issue 7, July-2013 44

ISSN 2229-5518

Synthesis and spectroscopic characterization of

some sterically hindered
µ-oxo bis [tricyclohexyl antimony (V)]
carboxylates and -halocarboxylates
Kiran Singhal*, Dharmendra K. Srivastava, Prem Raj

Abstract— A series of sterically hindered µ-oxo bis [tricyclohexylantimony (V)] carboxylates [(cyclo-C6H11)3Sb-O-Sb(cyclo-
C6H 11 ) 3 ](OCOR) 2 where -OCOR = p-trifluoromethyl mandelate, p-methoxy mandelate, salicyclate, 2pyrazine carboxylate, mandelate has
1 19 13
been synthesised and characterised by solid state infrared, H , Fand C NMR spectroscopy, molecular weight and conductance
measurements. The newly synthesized derivatives are monomeric in benzene and non ionic in acetonitrile with pentacoordination
dispensation around antimony.

1 19 13
Keywords—µ-oxo bis [tricyclohexylantimony (V)] carboxylates, halocarboxylates, IR, H, F NMR, CNMR spectra, monomeric, non ionic.

——————————  ——————————

1 INTRODUCTION
Despite a considerable amount of work done on the synthesis

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and reactivity of organoantimony (V) carboxylates, R n- 2 Results and Discussion
Sb(OCOR) 5-n (n= 1-4), R = alkyl, aryl, those having Sb-O-Sb The interaction of µ-oxy bis (tricyclohexyl antimony chloride)
framework have been studied to a limited extent [1-8]. The
[(cyclo-C 6 H 11 ) 3 SbCl] 2 O, with the silver salt of corresponding
latter class of compounds is important in the light of fact that
carboxylic acid in 1:1 and 1:2 molar ratio afforded mono and
sodium stibogluconate (pentostam) a well known drug for the
treatment of leishmainiasis have the similar framework cou- di-substituted µ-oxy bis (tricyclohexyl antimony) derivatives,
pled with gluconate constitution. Our recent in vitro an- respectively (Eq. 1-2).
tileishmaniasis and antimicrobial studies indicate that µ-
oxobis [(triarylantimony (V)] dicarboxylates exhibit high anti- 1:1
fungal, antibacterial, antitumoral and antileishmainial activity THF
[(cyclo-C6H11)3SbCl]2O + AgL (cyclo-C6H11)3Sb-O-Sb(cyclo-C6H11)3 + AgCl (1)
[9-15]. Since the biological activity is largely affected by the
nature of anion and organic group bound to the central metal
atom apart from its nature of metal, geometrical dispensation 1:2
Cl L

around metal and oxidation state, we considered it worth- THF

while to synthesize a series of µ-oxo bridged organoantimony [(cyclo-C6H11)3SbCl]2O + 2AgL (cyclo-C6H11)3Sb-O-Sb(cyclo-C6H11)3 + 2AgCl (2)
carboxylates and –halocarboxylates having biologically poten-
tial organic moieties. It may be noted that cyclohexyltin deriv- L L
atives exhibit potential antimicrobial and antitumoral activity. O
OH
In addition to this the introduction of cyclohexyl group is
C O OH
O O
F3 C C C
L= H 3CO C C
known to render the hydrolytic stability to the system [16-23]. OH
H O
H O

The present investigation concerned with the synthesis of µ- -OCOC6H 4(o-OH) 1, -OCOCH(OH)C6H4 (p-CF3) 2 -OCOCH(OH)C6H4(p-
oxobis [(tricyclohexylantimony (V)] dicarboxylates and their O
OCH3) 3

characterization by IR, NMR spectroscopy. Solution phase

OH O
N C
C C O
studies complementary to above have been carried out to as- Ph
O
N

-OCOC(OH)(C6H5)2 4 -OCOC4N 2H3 5

As is well known α-hydroxy carboxylic acid may unclog o
————————————————
• *Corrseponding author is Dr. (Mrs.) Kiran Singhal, Associate Professor,
Department of Chemistry, University of Lucknow, Lucknow, U.P., India- cyclisation using hydroxyl and carboxylic hydrogen's [23], β-
226007 and is Ph. D. supervisor of Mr. D. K. Srivastava. hydroxy, carboxylic acids normally prefer monodentate and
• Email: singhal.kiran@gmail.com, Ph: +91-9415159894
• Contract Grant Sponsor: University Grants Commission, New Delhi,
linear salts [24]. The only carboxylic acid undergoing cyclisa-
India Vide Letter No. 37-429/2009 SR. tion was mandelic acid to form cyclic µ-oxy-bis (tricyclohexyl
Dr. Prem Raj is Senior Professor Chemistry Departrment, Lucknow antimony) derivatives (7, 8), irrespective of molar ratio i.e. the
University, Lucknow, U. P., India.
same product was formed in 1:1 and 1:2 molar ratio reactions.
The formation of ring compound was established on the basis
certain the chemical behavior in solution. of amount of residue after filtration, melting points, elemental
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International Journal of Scientific & Engineering Research, Volume 4, Issue 7, July-2013 45
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analysis, super imposable IR spectra and other spectral analy- MHz FT NMR) in solvent (DMSO + CDCl 3 ) with chemical
sis. On the other hand, the other α-hydroxy acid viz. benzilic shift being reported as δ(ppm) taking tetramethylsilane as ref-
acid, p. (trifluoromethyl) mandelic acid, p-methoxy mandelic erence. The peak for protons of DMSO appeared at v 83.3
acid do not form the cyclometallates and mono or di- ppm. The 1HNMR data of the title compounds are listed in
Table-4. The chemical shifts of the protons of cyclohexyl ring
substituted oxo-bridged derivatives of antimony are formed
appear in the range δ(1.15 – 3.80) ppm in the form of multiplet.
for 1:2 and 1:2 molar ratio reactions, respectively. The appearance of signal of protons of cyclohexyl ring as mul-
THF
(cyclo-C6H11)3Sb O Sb(cyclo-C6H11)3 + AgCl (3) tiplet is due to low to high long range coupling .When four
[(cyclo-C6H11)3SbCl]2O + 2AgL/AgL
sigma bonds between interacting protons adopt a 'W-
O O arrangement' as in the case of 1, 3 diequitorial protons of a
O R rigid cyclohexyl system such type of coupling are observed
(fig. 1).
O
C O

HO C H
where L = C6H5CH(OH)COO-; R = C6H5-

-OCOCH(OH)C6H 5 6

Figure 1
The newly synthesized µ-oxy, derivatives of tricyclohexyl an- In other word this is due to diaxial, axial, equatorial and
timony (v) are white or off white crystalline solid with sharp diequitorial coupling of protons of rigid cyclohexyl system.

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melting points and are soluble in organic solvents. The com- All the axial and equatorial protons of cyclohexyl ring give
pounds are listed with their physical properties in Table-1. The signals at different δ-values. The signals for proton (H1) bond-
elemental analysis was found satisfactory and within permis- ed to ipso carbon of cyclohexyl ring appear in the range δ(3.60
sible limits. The data obtained are summarized in Table (3-5). – 3.80) ppm. The axial proton at position – 2 (H2a) and equato-
The molar conductance values of the compound in acetonitrile rial proton at position – 3 experienced the same electronic en-
(10−3 solution) were found in the appropriate value to show vironment and were found magnetically equivalent giving out
their non-conducting behavior in solution. The molecular the signal at same position in the range δ(1.75 – 1.85) ppm. In
weight and thus Vant Hoff factor 'i' determined cryoscopically this way, the signals for cyclohexyl protons were found in
in nitro benzene confirmed their monomeric nature. good agreement with those reported earlier [31, 32]. The α-
2.1 INFRARED SPECTRA hydroxy acids containing α-hydrogen (2-6, 9, 10) shows the
The infrared absorption for all the µ-oxy bis [tricyclo- proton signal for α-hydrogen in the range δ(4.95 – 5.15) ppm.
hexylantimony (v)] derivatives were recorded in the range In the case of compounds, the methoxy proton was observed
4000-400 cm−1 using KBr pellets on FT IR spectrophotometer at δ(3.78, 3.81) ppm, respectively, as singlet. The phenyl ring
(Shimadzu 8201/PC). The Characteristic absorption frequen- protons appear in the range δ(6.85 – 7.95) ppm as multiplet,
cies are listed in Table (3). Absorption associated with various the details are summarized in the Table (4). The three, mag-
internal modes of vibrations of µ-oxy bis [tricyclohexyl anti- netically non equivalent protons (H2, H3, H4) of 2-pyrazine
mony (v)] derivatives have been identified and indicate the carboxylate were observed at δ(9.0315), 8.75(d) and 8.85(d)
nature of bonding. Bond due to antimony – oxygen – antimo- ppm, respectively, the peaks of ligands are comparable with
ny (Sb – O – Sb) bond is at almost similar position in the range free carboxylic acids and with those of similar organometallic
740-725 cm−1 as strong to very strong band and come in the compounds reported earlier [23, 24, 28-40].
range of earlier published data [20, 25-26, 27]. The position of 2.3 13C NMR SPECTRA
13C NMR spectra of representative compounds were recorded
asymmetric and symmetric modes and separation (∆v) be-
tween them provides a method of assessing carboxylate coor- on 300 MHz FT NMR (Bruker DRX – 300) spectrometer operat-
dination modes. The non-conducting the monomeric nature ing at Ω75 MHz using CDCl 3 as solvent and reference (δ77.0)
and the absence of band at 1556, 1413 and 650 cm−1 due to car- ppm with chemical shift being reported as δ(ppm). The peaks
boxylate ion [28-31] in the IR spectra further rule out the pos- are compared, identified and are listed in Table-5.The chemical
sibility of an ionic structure. The ν (OH) for the compounds (1- shift of four magnetically non-equivalent of cyclohexyl ring
6, 9-10) was observed in the range 3465-3240 cm−1 as a weak or were observed at different δ-values in the region δ(23.03 –
medium hand. In case of mandelic acid derivatives (7, 8) 56.72) ppm. The ipso-carbon (C1) was more shielded in all
where the cyclic product was obtained due to participation of cases and the signal appears in the range δ(55.09 – 56.72) ppm.
hydrogen of carboxylate group and hydroxyl group, ν(OH) The chemical shift behaviour of carbon centers of phenyl ring
was not recorded. is also dependent on the pKa values of the carboxylic acids.
1
2.2 H NMR SPECTRA The signals for magnetically non-equivalent carbon centers of
The 1H NMR spectra of some derivatives of µ-oxy bis [tricy- ligand acid appeared at different δ-value; and the signal for
clohexyl antimony (v)] were recorded on Bruker DRX-300 (300 carboxyl (>C = O) carbon was observed in the range δ(165.1 –
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International Journal of Scientific & Engineering Research, Volume 4, Issue 7, July-2013 46
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174.75) ppm with a shiftment towards lower field in compari- acid (0.245 g, 1.0m mol) in THF (20 mL) afforded off white
son to that of free acid which indicates the participation of crystalline compound characterized as tricyclohexyl antimony
carboxylate group in the formation of Sb-O-C(O) bond. In case (V) salicyclate µ-oxo tricyclohexyl- antimony (v) chloride (1).
of compounds (3, 4, 6 – 8) the chemical sift values for α-c ap- 3.2 1:2 Molar Ratio Reaction of [(Cyclo –
pears in the range δ(73.02 – 81.60) ppm. These values are at C6H11)3SbCl]2O with silver salt of (RS) – Mandelic Ac-
lower field in comparison to free acids showing the deshield- id (8)
ing effect at α-carbon center due to the coordination of car-
boxylate group to antimony. The 2-pyrazine carboxylate de- In an inert atmosphere a solution of [(Cyclo – C 6 H 11 ) 3 SbCl] 2
rivatives give the distinct signals for magnetically non- (0.414g, 0.5m mol) and silver salt of (RS) mandelic acid
equivalent carbons. The 19F NMR spectra, in case of compound (0.259g, 1.0m mol) in THF (20 mL) was stirred at room tem-
(5, 6) which contains trifluoromethyl group was also recorded
perature for 24 h. The insoluble portion of heterogeneous solu-
and a signal appeared at δ62.9 ppm for fluorine atom. Thus,
tion containing precipitate of silver chloride was filtered. The
on the basis of molecular weight, conductivity, IR and NMR
(1H, 13C and 19F) spectral data, the µ-oxy bis [tricyclohexyl an- filtrate on concentration in vacuo followed by addition of pe-
timony (v)] derivatives prepared in the present investigation troleum ether (40-600C) afforded white crystalline solid. The
may be assigned a trigonal bipyramidal structure with a Sb-O- compound was crystallized from a mixture of benzene and
Sb linkage and on each antimony atom more electronegative petroleum ether (40-600C) in the ratio (1:2) and was character-
group are situated at apical position (fig. 1-2). The similar ized as cyclometalled (RS) - µ-oxy bis [tricyclohexyl antimony
structure has also been established for other µ-oxo, derivatives (V)] mandelate (8). Similarly, 1:1 molar ratio reaction [(Cyclo –
of antimony [9, 13, 15, 19, and 20]. C 6 H 11 ) 3 SbCl] 2 O (O.82gg, 1.0m mol, with silver salt of (RS)
3 EXPERIMENTAL mandelic acid (0.259 g, 1.0 mmol) in THF (20 mL) afforded the
Tricyclohexylantimony dichloride and µ-oxo bis [tricyclo-
hexylantimony (V)] chloride were prepared by the reported same cyclometallates (RS) - µ-oxy bis [tricyclohexyl antimony
(V)] mandelate (7).

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method [21]. The carboxylic acids (all form Aldrich) were used
in the form of their silver salts. IR spectra were recorded in
solid state, using KBr pellets, on FT-IR spectrophotometer 3.3 1:2 Molar Ratio Reaction of [(Cyclo – C6H11)3
(Schimadzu 8201 PC, Shimadzu Corporation Kyoto, Japan) SbCl]2O with silver salt of (RS) p – (Trifluoro methyl)
over the spectral range 4000-400 cm-1. 1H, 19F, and 13C NMR Mandelic Acid (5)
spectra were recorded on a Bruker spectrometer (Bruker Cor-
poration, US), using TMS, CF 3 COOH and CDCl 3 as reference, A heterogeneous solution of [(Cyclo – C 6 H 11 ) 3 SbCl] 2 O (0.415g,
respectively. The stoichiometry of compounds was established 0.5 m mol) and silver salt of (RS) – p – (trifluoromethyl) man-
by elemental analysis on a semimicro scale using an elemental delic acid (0.327 g, 1.0m mol) in THF (15 mL) was stirred to-
analyzer (Elementar Vario EL III, Carlo Erba 1108, Milan, Ita- gether at room temperature for 24h. The white precipitate of
ly). All the reactions of [(cyclo– C 6 H 11 ) 3 SbCl] 2 O with silver salt AgCl thus formed was filtered off. The filtrate on concentra-
of corresponding – carboxylic acids were performed under
tion under vacuum (2-3 mL) afforded while solid after addi-
dark condition in presence of inert atmosphere. The corre-
tion of petroleum ether (60-800C) (2mL). The solid compound
sponding silver salts of carboxylic acids were prepared from
their sodium salt by reaction with silver nitrate. Tetra hydro was crystallized from a mixture of THF and n-Hexane (1:3)
furan (THF), was distilled purified and dried under an inert and was characterized as µ-oxy bis [tricyclohexyl antimony
atmosphere from sodium – benzophenone. The typical exper- (V) p-(trifluoromethyl) mandelate] (5).
iments for some representative µ-oxy-bis [tricyclohexyl anti- In the similar fashion 1:1 molar ratio reaction of [(Cyclo –
mony (v)] carboxylates are given below and the further details C 6 H 11 ) 3 SbCl] 2 O (0.829g, 1.0m mol) and silver salt of p-
for the other reactions are summarized in Table (1). The ana- (trifluoromethyl) mandelic acid (0.327g, 1.0m mol) in THF (20
lytical data are listed in Tables (2-5). mL) afforded the compound (RS) tricyclohexyl antimony (V)
3.1 1:2 Molar Ratio Reaction of [(Cyclo –
p-(trifluoromethyl) mandelate µ-oxo-tricyclohexylantimony
C 6 H 11 ) 3 SbCl] 2 O with silver salt of Salicylic Acid (2)
A solution of [(Cyclo – C 6 H 11 ) 3 SbCl] 2 O (0.829g, 1.0 mmol) and (V) chloride (6).
silver salt of salicylic acid (0.490g, 2.0m mol) in THF (25 mL)
was stirred at room temperature for 24h. On filtration of het- 3.4 1:2 Molar Ratio Reaction of [(Cyclo –
erogeneous solution containing precipitate of silver chloride, a C 6 H 11 ) 3 SbCl] 2 O with silver Salt of 2-Pyrazine carbox-
clear solution was obtained which was concentrated in vacuo ylic acid (11)
(2-3 mL). After the addition of n-hexane (3 mL), the solution
was allowed to stand overnight at O0C affording a white crys- In an oxygen and moisture tree atmosphere, a solution of
talline solid which was recrystallised from a mixture of THF [(Cyclo-C 6 H 11 ) 3 SbCl] 2 O (O.829g, 1.0m mol) with silver salt of
and n-Hexane (1:3). The Compound was characterized as µ- 2-Pyrazine carboxylic acid (0.462 of, 1.0m mol) in dry acetone
oxy bis [tricyclohexylantimony (v)] (salicyclate)] (1). In the (20 mL) was stirred at room temperature for 12h followed by
same manner, 1:1 molar ratio reaction of [(Cyclo- refluxion for 2h. The silver chloride thus formed was filtered
C 6 H 11 ) 3 SbCl] 2 O (0.829g, 1.0m mol) with silver salt of salicylic off and filtrate on concentration in vacuao (2mL) was stirred at
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room temperature for 12h followed by addition of petroleum TABLE – 1 Preparation and Properties of µ-Oxy bis [tricyclohexyl antimony (v)]

ether (60-800C) (3mL), yielded white crystalline/4-hexane mix-

derivatives

ture (1:3) to afford µ-oxybis [tricyclohexylantimony (V) (2- Comp. Complex

No.
[Cyclo-
C6H11)3
Ligand No. (g) Molar Ratio/ M.P.
Solvent (0C)
Colour Recrystalization
Solvent
pyrazine carboxylate)] (11). (1) [(cyclo-C6H11)3Sb]2O(Cl)(OCOC6H4OH-o)
SbCl]2O
0.829g 1, (0.245) 1:1 /THF 142 White n-Hexane
Benzene
4 FIGURES (2) [(cyclo-C6H11)3Sb]2O(OCOC6H4OH-o)2 0.829g 1, (0.490) 1:2 /THF 165 off white THF/n-Hexane

(3) [(cyclo-C6H11)3Sb]2O[OCOC(OH)(C6H5)2]2 0.414g 4, (0.335) 1:2 /THF 115 White THF Pet-ether
Figure 1 (40-600)

(4) [(cyclo-C6H11)3Sb]2O(Cl)[OCOC(OH)(C6H5)2] 0.829g 4, (0.335) 1:1/ THF 98 White THF,

L n-Hexane
(5) [(cyclo-C6H11)3Sb]2O[OCOCH(OH)C6H4CF3-p]2 0.415g 2, (0.327) 1:2/ THF 122 white THF, n-
(cyclo-C6H11) Hexane

(cyclo-C6H11) Sb (6) [(cyclo-C6H11)3Sb]2O(Cl)[OCOCH(OH)C6H4CF3-p] 0.829g 2, (0.327) 1:1/ THF 119 White THF,
n-Hexane
(cyclo-C6H11) Where L=o-OH-C6H4COO-,(C6H5)2C(OH)COO- (7) [(cyclo-C6H11)3Sb]2O[OCOCH(O)C6H5]** 0.829g 6, (0.259) 1:1 /THF 98 White Benzene/
O R' = p-CF3C6H4-, p-CH3O-C6H4- & 2pyrazine Pet. ether
(40-600C)
carboxylate (8) [(cyclo-C6H11)3Sb]2O[OCOCH(O)C6H5]** 0.414g 6, (0.259) 1:2/ THF 98 White Pet. Ether(40-
(cyclo-C6H11) 0
60 C)

(cyclo-C6H11) Sb
(9) [(cyclo-C6H11)3Sb]2O[OCOCH(OH)C6H4OCH3-p]2 0.414g 4, (0.290) 1:2 /THF 135 off white Acetone,
(cyclo-C6H11) n-Hexane
(10) [(cyclo-C6H11)3Sb]2O(Cl)[OCOCH(OH)C6H4OCH3-p] 0.414g 4, (0.145) 1:1/ THF 85 off white Acetone/ n-
L hexane
(11) [(cyclo-C6H11)3Sb]2O(OCOC4N2H3)2* 0.829g 5, (0.462) 1:2/Acetone 127 white Chloroform,
n-Hexane
*OCOC4N2H3 = 2-pyrazine carboxylate

Fig 1 Showing structure of µ-Oxo derivatives

** = cyclometallates

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Figure 2

(cyclo-C6H11) (cyclo-C6H11) TABLE – 2 Elemental Analysis of µ-oxy bis [tricyclohexyl antimony (v)] Derivatives
(cyclo-C6H11)
(cyclo-C6H11) Comp. Empirical Formula Molecular weight Found (Calcd.)%
Sb O Sb
(cyclo-C6H11) (cyclo-C6H11) No. C H N
O O
C (1) C43H71ClO4Sb2 930.99 55.50 (55.47) 7.59 (7.69) -
(2) C50H76O7Sb2 1032.65 63.35 (63.38) 7.39 (7.42) -
O
(3) C64H88O7Sb2 1212.90 63.35 (63.38) 7.38 (7.31) -

Fig 2 Showing structure of µ-Oxo Cyclometallate derivatives (4) C50H77ClO4Sb2 1021.12 58.51 (58.81) 7.52 (7.60) -
(5) C54H78F6O7Sb2 1196.70 54.31 (54.20) 6.53 (6.57) -
5 TABLES
(6) C45H72ClF3O4Sb2 1013.02 53.25 (53.35) 7.25 (7.16) -
(7) C44H72O4Sb2 908.56 58.25 (58.17) 7.87 (7.99) -
(8) C44H72O4Sb2 1120.76 57.88 (57.87) 7.60 (7.55) -
(9) C45H75ClO5Sb2 975.05 55.35 (55.43) 7.70 (7.75) -
(11) C46H72N4O5Sb2 1004.61 54.98 (55.00) 7.18 (7.22) 5.57 (5.58)

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TABLE – 3 Characteristic TR Absorption of µ-oxy-bis [tricyclohexyl antimony (V)] TABLE – 4 1H NMR Spectral Data for µ-Oxybis [tricyclohexyl antimony (v)] Derivatives in δ(ppm)

Derivatives in cm−1 Comp. Cyclohexyl Ligand

No. H1 H2e H2a/H3a H3e H4e H4a H2' H3' H4' OCH3 Hα
Comp. ν(OCO) ν(OH) ν(Sb-C) ν (Sb-O-
(2) 3.75-3.81 2.80-2.88 1.71-1.75 1.52-1.55 1.57-1.61 1.16-1.24 7.48-7.77 6.51-6.60 7.02-7.08 - -
No. νasym νsym ∆ν γ-mode Sb)
(m) (m) (m) (m) (m) (m)
1 1635 (s) 1390 (vs) 245 3287 (m) 459 (m) 742 (s) (3) 3.80-3.85 2.91-2.87 1.73-1.78 1.52-1.56 1.18-1.20 1.19-1.25 7.25-7.48 7.14-7.17 (m) - -
2 1637 (m) 1309 (s) 328 3280 (m) 459 (m) 745 (s) (m) (m) (m) (m) (m) (m) (m)
3 1686 (s) 1303 (m) 383 3425 (w) 456 (s) 731 (s) (4) 3.77-3.80 2.82-2.89 1.71-1.77 1.54-1.58 1.60-1.65 1.16-1.21 7.23-7.74 7.10-7.12 (m) - -

1682 (s) 1310 (w) 372 3431 (w) 455 (m) 735 (s) (m) (m) (m) (m) (m) (m) (m)
4
(5) 3.79-3.83 2.82-2.90 1.72-1.76 1.53-1.58 1.61-1.64 1.16-1.19 7.40-7.78 (m) - - 5.37 (s)
5 1686 (s) 1321 (s) 365 3461 (w) 451 (m) 728 (vs)
(m) (m) (m) (m) (m) (m)
6 1690 (s) 1325 (vs) 365 3463 (w) 456 (s) 736 (vs)
(7) & 3.64-3.69 2.70-2.81 1.70-1.76 1.55-1.62 1.64-1.68 1.13-1.20 7.34-7.59 7.13-7.18 (m) - 5.28 (s)
7 1684 (s) (O) - - 458 (s) 731 (vs) (8) (m) (m) (m) (m) (m) (m)
8 1684 (s) 1304 380 - 458 (s) 731 (vs) (9) 3.81-3.85 2.89-2.95 1.73-1.79 1.51-1.57 1.60-1.63 1.14-1.19 7.45-7.82 (m) - 3.80 (s) 5.34 (s)
9 1687 (s) 1315 (vs) 372 3449 (w) 454 (s) 735 (s) (m) (m) (m) (m) (m) (m)

10 1687 (s) 1301 (m) 386 3449 (s) 459 (s) 738 (vs) Where m = multiplet; d = doublet; s = singlet

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O O
O O
11 1660 (vs) 1327 (vs) 333 - 456 (s) 738 (s) H

H
H1
HO
C
Hα HO
C
Hα

H3a
Where, w = weak, m = medium, s = strong, vs = very strong, O = overlapped H

Sb 2' 2'
eH4
H2e
3' 3'
H
4' 4'
eH3
H4a OCH3
H2a
Carboxylate ligand attached with antimony
Cylohexyl group attached with antimony

TABLE – 5 13C NMR Spectral Data for µ-oxybis [tricyclohexylantimony (V)] derivatives in δ ppm

Comp. Cyclohexyl Ligand

No. C1 C2 C3 C4 Cα >C=0 C1' C2' C3' C4'
(2) 55.43 30.01 26.14 26.00 - 173.09 141.52 130.54, 116.98 & 134.83
161.48 (OH) 118.56
(3) 55.09 29.61 26.34 26.02 81.58 174.61 143.02 127.73 127.28 127.32
(7) & (8) 55.31 29.63 28.23 25.90 73.68 174.13 139.71 128.26 126.58 127.46
(6) 55.24 29.45 28.20 25.87 73.02 173.14 139.85 126.44 126.49 128.06
(11) 56.58 28.05 25.03 25.55 - 165.01 145.61 143.98 144.53 197.66

# 19F NMR Spectra for compound (S) gave the signal at δ62.9 ppm for − CF3 group

O
O
Sb C
1 HO H
α O

1' N C
3 2 O
4 2' 2'

3' 4' 3'

N
Cyclohexyl group directly attached with antimony 4'

Carboxylate ligands attached with antimony

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International Journal of Scientific & Engineering Research, Volume 4, Issue 7, July-2013 46
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174.75) ppm with a shiftment towards lower field in compari- acid (0.245 g, 1.0m mol) in THF (20 mL) afforded off white
son to that of free acid which indicates the participation of crystalline compound characterized as tricyclohexyl antimony
carboxylate group in the formation of Sb-O-C(O) bond. In case (V) salicyclate µ-oxo tricyclohexyl- antimony (v) chloride (1).
of compounds (3, 4, 6 – 8) the chemical sift values for α-c ap- 3.2 1:2 Molar Ratio Reaction of [(Cyclo –
pears in the range δ(73.02 – 81.60) ppm. These values are at C6H11)3SbCl]2O with silver salt of (RS) – Mandelic Ac-
lower field in comparison to free acids showing the deshield- id (8)
ing effect at α-carbon center due to the coordination of car-
boxylate group to antimony. The 2-pyrazine carboxylate de- In an inert atmosphere a solution of [(Cyclo – C 6 H 11 ) 3 SbCl] 2
rivatives give the distinct signals for magnetically non- (0.414g, 0.5m mol) and silver salt of (RS) mandelic acid
equivalent carbons. The 19F NMR spectra, in case of compound (0.259g, 1.0m mol) in THF (20 mL) was stirred at room tem-
(5, 6) which contains trifluoromethyl group was also recorded
perature for 24 h. The insoluble portion of heterogeneous solu-
and a signal appeared at δ62.9 ppm for fluorine atom. Thus,
tion containing precipitate of silver chloride was filtered. The
on the basis of molecular weight, conductivity, IR and NMR
(1H, 13C and 19F) spectral data, the µ-oxy bis [tricyclohexyl an- filtrate on concentration in vacuo followed by addition of pe-
timony (v)] derivatives prepared in the present investigation troleum ether (40-600C) afforded white crystalline solid. The
may be assigned a trigonal bipyramidal structure with a Sb-O- compound was crystallized from a mixture of benzene and
Sb linkage and on each antimony atom more electronegative petroleum ether (40-600C) in the ratio (1:2) and was character-
group are situated at apical position (fig. 1-2). The similar ized as cyclometalled (RS) - µ-oxy bis [tricyclohexyl antimony
structure has also been established for other µ-oxo, derivatives (V)] mandelate (8). Similarly, 1:1 molar ratio reaction [(Cyclo –
of antimony [9, 13, 15, 19, and 20]. C 6 H 11 ) 3 SbCl] 2 O (O.82gg, 1.0m mol, with silver salt of (RS)
3 EXPERIMENTAL mandelic acid (0.259 g, 1.0 mmol) in THF (20 mL) afforded the
Tricyclohexylantimony dichloride and µ-oxo bis [tricyclo-
hexylantimony (V)] chloride were prepared by the reported same cyclometallates (RS) - µ-oxy bis [tricyclohexyl antimony
(V)] mandelate (7).

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method [21]. The carboxylic acids (all form Aldrich) were used
in the form of their silver salts. IR spectra were recorded in
solid state, using KBr pellets, on FT-IR spectrophotometer 3.3 1:2 Molar Ratio Reaction of [(Cyclo – C6H11)3
(Schimadzu 8201 PC, Shimadzu Corporation Kyoto, Japan) SbCl]2O with silver salt of (RS) p – (Trifluoro methyl)
over the spectral range 4000-400 cm-1. 1H, 19F, and 13C NMR Mandelic Acid (5)
spectra were recorded on a Bruker spectrometer (Bruker Cor-
poration, US), using TMS, CF 3 COOH and CDCl 3 as reference, A heterogeneous solution of [(Cyclo – C 6 H 11 ) 3 SbCl] 2 O (0.415g,
respectively. The stoichiometry of compounds was established 0.5 m mol) and silver salt of (RS) – p – (trifluoromethyl) man-
by elemental analysis on a semimicro scale using an elemental delic acid (0.327 g, 1.0m mol) in THF (15 mL) was stirred to-
analyzer (Elementar Vario EL III, Carlo Erba 1108, Milan, Ita- gether at room temperature for 24h. The white precipitate of
ly). All the reactions of [(cyclo– C 6 H 11 ) 3 SbCl] 2 O with silver salt AgCl thus formed was filtered off. The filtrate on concentra-
of corresponding – carboxylic acids were performed under
tion under vacuum (2-3 mL) afforded while solid after addi-
dark condition in presence of inert atmosphere. The corre-
tion of petroleum ether (60-800C) (2mL). The solid compound
sponding silver salts of carboxylic acids were prepared from
their sodium salt by reaction with silver nitrate. Tetra hydro was crystallized from a mixture of THF and n-Hexane (1:3)
furan (THF), was distilled purified and dried under an inert and was characterized as µ-oxy bis [tricyclohexyl antimony
atmosphere from sodium – benzophenone. The typical exper- (V) p-(trifluoromethyl) mandelate] (5).
iments for some representative µ-oxy-bis [tricyclohexyl anti- In the similar fashion 1:1 molar ratio reaction of [(Cyclo –
mony (v)] carboxylates are given below and the further details C 6 H 11 ) 3 SbCl] 2 O (0.829g, 1.0m mol) and silver salt of p-
for the other reactions are summarized in Table (1). The ana- (trifluoromethyl) mandelic acid (0.327g, 1.0m mol) in THF (20
lytical data are listed in Tables (2-5). mL) afforded the compound (RS) tricyclohexyl antimony (V)
3.1 1:2 Molar Ratio Reaction of [(Cyclo –
p-(trifluoromethyl) mandelate µ-oxo-tricyclohexylantimony
C 6 H 11 ) 3 SbCl] 2 O with silver salt of Salicylic Acid (2)
A solution of [(Cyclo – C 6 H 11 ) 3 SbCl] 2 O (0.829g, 1.0 mmol) and (V) chloride (6).
silver salt of salicylic acid (0.490g, 2.0m mol) in THF (25 mL)
was stirred at room temperature for 24h. On filtration of het- 3.4 1:2 Molar Ratio Reaction of [(Cyclo –
erogeneous solution containing precipitate of silver chloride, a C 6 H 11 ) 3 SbCl] 2 O with silver Salt of 2-Pyrazine carbox-
clear solution was obtained which was concentrated in vacuo ylic acid (11)
(2-3 mL). After the addition of n-hexane (3 mL), the solution
was allowed to stand overnight at O0C affording a white crys- In an oxygen and moisture tree atmosphere, a solution of
talline solid which was recrystallised from a mixture of THF [(Cyclo-C 6 H 11 ) 3 SbCl] 2 O (O.829g, 1.0m mol) with silver salt of
and n-Hexane (1:3). The Compound was characterized as µ- 2-Pyrazine carboxylic acid (0.462 of, 1.0m mol) in dry acetone
oxy bis [tricyclohexylantimony (v)] (salicyclate)] (1). In the (20 mL) was stirred at room temperature for 12h followed by
same manner, 1:1 molar ratio reaction of [(Cyclo- refluxion for 2h. The silver chloride thus formed was filtered
C 6 H 11 ) 3 SbCl] 2 O (0.829g, 1.0m mol) with silver salt of salicylic off and filtrate on concentration in vacuao (2mL) was stirred at
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International Journal of Scientific & Engineering Research, Volume 4, Issue 7, July-2013 50
ISSN 2229-5518

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