Syntheses and structures of two complexes with incomplete cuboidal Mo3Te44+ and Mo3(μ3-S)Te34+ cluster cores

Article abstract of DOI:10.1016/S0277-5387(00)00334-X

The reaction of tributylphosphine, benzoic acid and Mo₃Te₇(S₂P(OPr(i))₂)₃I produced a new compound with triangular cluster skeleton Mo₃Te₄⁴⁺, Mo₃Te₄[S₂P(OPr(i))₂]₃(μ-PhCO₂)PBu₃ (1). An unexpected compound including an Mo₃Te₃S⁴⁺ skeleton, Mo₃(μ₃-S)Te₃-[S₂P(OPr(i))₂]₃(μ-PhNH₂CO₂)PBu₃ (2), was obtained using aminobenzoic acid instead of benzoic acid. X-ray crystallographic analysis revealed that these complexes belong to the Mo₃E₄⁴⁺ (E = S, Se, Te) incomplete cuboidai cluster family and are dimeric through the Te···Te interaction. ¹H and ³¹P NMR and IR spectroscopic data were also used to characterize these compounds. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0277-5387(00)00334-X

www.elsevier.nl/locate/poly
Polyhedron 19 (2000) 925–929
Syntheses and structures of two complexes with incomplete cuboidal
4q
Mo3Te44q and Mo3(m3-S)Te3 cluster cores
*
Xiang Lin, Hua-Yang Chen, Li-Sheng Chi, Can-Zhong Lu, Hong-Hui Zhuang
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou,
Fujian 350002, People’s Republic of China
Received 16 November 1999; accepted 14 February 2000
Abstract
The reaction of tributylphosphine, benzoic acid and Mo3Te7(S2P(OPri)2)3I produced a new compound with triangular cluster skeleton
Mo3Te44q, Mo3Te4[S2P(OPri)2]3(m-PhCO2)PBu3 (1). An unexpected compound including an Mo3Te3S4q skeleton, Mo3(m3-S)Te3-
[S2P(OPri)2]3(m-PhNH2CO2)PBu3 (2), was obtained using aminobenzoic acid instead of benzoic acid. X-ray crystallographic analysis
revealed that these complexes belong to the Mo3E44q (EsS, Se, Te) incomplete cuboidal cluster family and are dimeric through the Te∆Te
interaction. 1H and 31P NMR and IR spectroscopic data were also used to characterize these compounds.
All rights reserved.
q2000 Elsevier Science Ltd
Keywords: Cluster compounds; Molybdenum complexes; Tellurium-rich compounds; De-tellurium reaction; Crystal structures
1. Introduction
m-Te ligands, making it potentially a good precursor for other
tellurido cluster compounds.
A convenient route to the M3(m3-E)(m-E)34q (MsMo,
Intensive studies have been carried out on molybdenum/
tungsten chalcogenide clusters since 1985 [1–5]. Compared
with sulfides and selenides, the chemistry of tellurido com-
plexes of molybdenum and tungsten is much less developed
because many traditional reagents applicable to Mo/W–S/
Se systems are not simply transferable to the Mo/W–Te sys-
tem, and limited progress has been made in the exploration
of effective reagents or starting materials [6]. Until recently,
only a few such Mo/W–Te clusters, including the triangular
4q
W; EsS, Se) cluster by reaction of M3(m3-E)(m-E2)3
cluster compounds with phosphine or cyanide has been
reported [12–15]. Saito and co-workers considered that the
Mo3Te74q fragment has an extraordinary stability in aqueous
cyanide or in CH3OH with PEt3 [7]. However, our experi-
4q
ments showed that the Mo3Te7 cluster core is stable in
CH2Cl2 with PPh3, and the reaction of Mo3Te7-
[S2P(OPri)2]3I with tributylphosphine leads to transforma-
4q
4q
tion of the Mo3Te7 core to the Mo3Te4 core. Another
very interesting result in our experiments is that aromatic
acids might have different effects on the transformation of
cluster complex Cs4.5[Mo3Te7(CN)6]I2.5P3H2O [7] with
4q
an Mo3(m3-Te)(m-Te2)3
core, the tetrahedral clusters
K7[Mo4Te4(CN)12]PH2O and K6[W4Te4(CN)12]P5H2O
4q
nq
the Mo3Te7 cluster core to produce a Te-capping or S-
containing the M4(m3-Te)4
(ns5, 6) cuboidal core
[8–10], and the octahedral cluster [Na(Py)6]q-
[W6Te8(Py)6]yPPy and W6Te8(PiP)6P6PiP with a W6Te8
core [11], have been reported. However, the absence of the
Mo3Te4 type cluster, of which the sulfide and selenide ana-
logues have been well studied, has drawn our attention to
conversion of the Mo3Te7 cluster core to Mo3Te4. In com-
parison with those compounds containing Mo3Te7, Mo4Te4
or W6Te8 cores, the compound with an Mo3Te4 core has
higher reactivity since it possesses a vacant subsite and three
capping triangular cluster core, which has never been
observed in previous studies in this field. Herein we report
the syntheses and molecular structures of two cluster com-
pounds containing Mo3Te44q and Mo3(m3-S)Te34q cores.
2. Experimental
All manipulationswerecarriedoutunderdinitrogenatmos-
phere using standard Schlenk techniques. The solvents were
degassed prior to use. Other materials were reagent-grade
purity and used without further purification. The 31P NMR
* Corresponding author. Tel.: q86-591-3711368; fax: q86-591-
3714946; e-mail: zhh@ms.fjirsm.ac.cn
0277-5387/00/$ - see front matter q2000 Elsevier Science Ltd All rights reserved.
PII S0277-5387(00)00334-X
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Table 1
Crystallographic data for Mo3Te4[S2P(OPri)2]3(m-PhCO2)PBu3 and Mo3(m3-S)Te3[S2P(OPri)2]3(m-PhNH2CO2)PBu3
Formula
FW
Mo3Te4S6P4O8C37H74
1762.42
C2/c
29.8261(3)
16.4363(3)
26.6482(6)
90
Mo3Te3S7P4O8C37NH75
1680.9
P1
¯
Space group
˚
a (A)
15.9465(2)
16.0576(1)
16.3111(3)
103.508(1)
115.859(1)
100.141(1)
3465.19(8)
2
˚
b (A)
˚
c (A)
a (8)
b (8)
96.218(1)
90
12986.9(6)
8
1.803
2.664
7.95, 17.24
g (8)
3
˚
V (A )
Z
Dcalc (g cmy3
)
1.611
2.112
m (mmy1
)
R1, wR2 (%) a
8.66, 20.24
wy1ss2(Fo2)q(0.1149P)2
Weighting scheme b
wy1ss2(Fo2)q(0.0858P)2q82.0874P
a
2
2
2
2 2
x
wR2s 8w(Fo yFc ) /8w(Fo ) .
2
2
b Ps(Fo q2Fc )/3.
spectra were obtained on a Varian Unity-500 spectrometer in
CH2Cl2 solutions with 80% H3PO4 as external standard in a
31P{1H} mode. UV–Vis spectra were recorded on a Varian
Cary-2390 spectrophotometer in CH2Cl2 solutions. IR spec-
tra were recorded on a Nicolet Magna 750 FT-IR spectro-
photometer using KBr pellets (4000–500 cmy1) and CsI
pellets (600–120 cmy1). Element analyses were carried out
by the Elemental Analysis Laboratory in our institute.
Preparation of Mo3Te4S6P4O8C37H74 (1): 0.195 g (0.1
mmol) Mo3Te7(S2P(OPri)2)3I, which was prepared accord-
ing to the literature [16], 0.018 g (0.15 mmol) benzoic acid
and 0.3 ml tributylphosphine were heated in 30 ml mixed-
solvent of CH2Cl2–C2H5OH at 408C for 3 h. The black crys-
tals were isolated after the solution was allowed to stand for
4 days (0.072 g, yield 41%). Anal. Calc. for Mo3Te4-
[S2P(OPri)2]3(m-PhCO2)PBu3: C, 25.23; H, 4.23. Found:
C, 25.05; H, 4.29%. IR (KBr pellet, cmy1): n 1600, 1510
(CO), 716, 677 (C6H5). UV–Vis (CH2Cl2, nm): l 370, 620.
31P NMR (200 MHz, CH2Cl2, H3PO4): d 111.7, 85.2, 22.3.
The preparation procedure of Mo3Te3S7P4O8C37NH75 (2)
was the same as for complex 1 except that 2-aminobenzoic
acid was used instead of benzoic acid (0.053 g, yield 32%).
Anal. Calc. for Mo3(m3-S)Te3[S2P(OPri)2]3(m-PhNH2-
CO2)PBu3: C, 26.44; H, 4.5; N, 0.83. Found: C, 26.62; H,
4.91; N, 0.88%. IR (KBr pellet, cmy1): n 1614, 1498 (CO),
3361 (NH2), 667 (C6H5), 414 (Mo–(m3-S)). UV–Vis
(CH2Cl2, nm): l 337, 580. 31P NMR (200 MHz, CH2Cl2,
H3PO4): d 106.0, 85.6, 17.8.
the SHELXTL-5 program package [18]. The crystallo-
graphic data and refinement parameters are listed in Table 1.
3. Discussion
3.1. Synthesis
The preparation of complex 1, Mo3Te4[S2P(OPri)2]3(m-
PhCO2)PBu3, using the abstraction of tellurium from an
Mo3Te74q cluster core to generate Mo3Te44q, is very similar
to the preparation of the sulfide and selenide analogues, in
which the bridging ligand is benzoic acid. This reaction can
be completed at ambient temperature within a few hours. The
preparation of complex 2, Mo3(m3-S)Te3[S2P(OPri)2]3(m-
PhNH2CO2)PBu3, is similar to that of 1, except that 2-ami-
nobenzoic acid was employed instead of benzoic acid, and
the capping tellurium atom of the cluster core was substituted
by sulfur in complex 2, which might originate from the
decomposition of the DTP (dialkyldithiophosphinate)
ligand. It seems plausible that there is ‘competition’ between
sulfur and tellurium to occupy the cap site in solution, and
the nature of the bridging ligand might affect the structure of
the final product. We found that the formation of the
Mo3Te3S4q skeleton was not an incidental event since we
could repeat this experiment very well. Furthermore, byusing
4-aminobenzoic acid instead of 2-aminobenzoic acid, a sim-
ilar product can be obtained, in which the position of 2-
aminobenzoic acid was replaced by 4-aminobenzoic acid but
the cluster core was still Mo3Te3S4q [19]. These compounds
are mildly air sensitive, and when their solutions were
exposed in air for several days, a tellurium mirror at the
bottom of the receptacles was found along with some dark-
brown crystals, which proved to be Mo3Te7[S2P(OPri)2]3I
by IR spectra and X-ray diffraction experiments. Thereaction
scheme can be represented as shown in Scheme 1.
2.1. X-ray crystallography
The crystal data of complexes 1 and 2 were collected on a
Siemens SMART CCD area detector diffractometer using
˚
graphite-monochromated Mo Ka radiation (ls0.71073 A)
at 293 K, and empirical absorption correction by SADABS
[17] was applied to the intensity data. Structure solution and
refinement were performed on a SGIINDYworkstationusing
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X. Lin et al. / Polyhedron 19 (2000) 925–929
927
Table 3
˚
Selected interatomic distances (A) and and angles (8) in Mo3(m3-S)Te3-
[S2P(OPri)2]3(m-PhNH2CO2)PBu3 (2)
Mo(1)–S(7)
Mo(1)–Te(2)
Mo(1)–Te(1)
Mo(1)–S(2)
Mo(1)–S(1)
Mo(1)–P(4)
Mo(1)–Mo(3)
Mo(1)–Mo(2)
Mo(2)–O(8)
Mo(2)–S(7)
Mo(2)–S(3)
2.384(4)
2.633(2)
2.646(2)
2.657(5)
2.659(5)
2.675(5)
2.900(2)
2.921(2)
Mo(2)–S(4)
Mo(2)–Te(1)
Mo(2)–Te(3)
Mo(2)–Mo(3)
Mo(3)–O(7)
Mo(3)–S(7)
Mo(3)–S(6)
Mo(3)–S(5)
2.623(5)
2.647(2)
2.687(2)
2.822(2)
2.232(10)
2.364(4)
2.562(4)
2.641(5)
2.644(2)
2.679(2)
3.140(2)
Scheme 1.
3.2. Structure
2.261(11) Mo(3)–Te(2)
2.358(4)
2.571(4)
Mo(3)–Te(3)
Te(3)–Te(3)a1 a
The structures of cluster molecules 1 and 2 are shown in
Fig. 1, and selected bond distances and angles are listed in
Tables 2 and 3, respectively.
In complex 1, the three molybdenum atoms define an
approximate isosceles triangle with Mo–Mo distances of
S(7)–Mo(1)–Te(2) 107.57(12) S(3)–Mo(2)–Te(1)
S(7)–Mo(1)–Te(1) 106.38(11) S(4)–Mo(2)–Te(1)
Te(2)–Mo(1)–Te(1) 97.71(6) O(8)–Mo(2)–Te(3)
S(7)–Mo(1)–S(2)
Te(2)–Mo(1)–S(2) 162.87(13) S(3)–Mo(2)–Te(3) 159.37(12)
Te(1)–Mo(1)–S(2)
S(7)–Mo(1)–S(1)
Te(2)–Mo(1)–S(1)
97.77(12)
88.24(12)
83.5(3)
83.5(2)
S(7)–Mo(2)–Te(3) 111.31(11)
˚
2.940(2), 2.970(2) and 2.832(2) A, respectively, of which
91.41(12) S(4)–Mo(2)–Te(3)
82.4(2) Te(1)–Mo(2)–Te(3) 91.56(5)
93.10(12) O(7)–Mo(3)–S(7)
84.77(11)
the shortest side is bridged by a PhCO2y ligand. The average
˚
82.7(3)
84.5(3)
83.9(2)
81.5(3)
156.8(2)
77.7(2)
Mo–Mo distance of 2.914 A is slightly longer than the value
Te(1)–Mo(1)–S(1) 163.15(13) O(7)–Mo(3)–S(6)
˚
of 2.891 A in Cs4.5[Mo3Te7(CN)6]I2.5P3H2O [7] and 2.889
S(2)–Mo(1)–S(1)
S(7)–Mo(1)–P(4)
Te(2)–Mo(1)–P(4)
Te(1)–Mo(1)–P(4)
S(2)–Mo(1)–P(4)
S(1)–Mo(1)–P(4)
O(8)–Mo(2)–S(7)
O(8)–Mo(2)–S(3)
S(7)–Mo(2)–S(3)
O(8)–Mo(2)–S(4)
S(7)–Mo(2)–S(4)
S(3)–Mo(2)–S(4)
75.1(2)
164.1(2)
82.12(14) S(7)–Mo(3)–S(5)
S(7)–Mo(3)–S(6)
O(7)–Mo(3)–S(5)
Table 2
˚
Selected interatomic distances (A) and angles (8) in Mo3Te4-
84.1(2)
84.4(2)
84.6(2)
82.9(3)
84.3(3)
83.5(2)
82.6(3)
156.9(2)
77.2(2)
S(6)–Mo(3)–S(5)
O(7)–Mo(3)–Te(2) 169.5(3)
S(7)–Mo(3)–Te(2) 107.82(11)
S(6)–Mo(3)–Te(2)
S(5)–Mo(3)–Te(2)
O(7)–Mo(3)–Te(3)
S(7)–Mo(3)–Te(3) 111.38(11)
S(6)–Mo(3)–Te(3) 160.06(13)
[S2P(OPri)2]3(m-PhCO2)PBu3 (1)
Mo(1)–Te(2)
Mo(1)–Te(1)
Mo(1)–P(4)
Mo(1)–S(1)
Mo(1)–S(2)
Mo(1)–Te(4)
Mo(1)–Mo(3)
Mo(1)–Mo(2)
Mo(2)–O(7)
Mo(2)–S(3)
Mo(2)–S(4)
2.606(2)
2.612(2)
2.615(5)
2.630(5)
2.636(5)
2.663(2)
2.946(2)
2.972(2)
Mo(2)–Te(1)
Mo(2)–Te(4)
Mo(2)–Te(3)
Mo(2)–Mo(3)
Mo(3)–O(8)
Mo(3)–S(6)
Mo(3)–S(5)
Mo(3)–Te(2)
2.608(2)
2.637(2)
2.639(2)
2.831(2)
2.207(10)
2.529(5)
2.577(5)
2.597(2)
2.648(2)
2.649(2)
3.103(2)
97.08(12)
88.58(11)
84.9(3)
S(5)–Mo(3)–Te(3)
Te(2)–Mo(3)–Te(3) 90.45(5)
84.12(11)
O(8)–Mo(2)–Te(1) 169.9(3)
S(7)–Mo(2)–Te(1) 107.11(11)
2.216(11) Mo(3)–Te(4)
a Symmetry transformations used to generate equivalent atoms: a1: yxq1,
yyq1, yzq1.
2.540(5)
2.576(5)
Mo(3)–Te(3)
Te(3)–Te(3)a1 a
Te(2)–Mo(1)–P(4)
81.26(13) S(4)–Mo(2)–Te(4) 155.66(13)
Te(2)–Mo(1)–Te(1) 100.68(6) Te(1)–Mo(2)–Te(4) 108.42(6)
P(4)–Mo(1)–Te(1)
Te(2)–Mo(1)–S(1)
P(4)–Mo(1)–S(1)
Te(1)–Mo(1)–S(1) 160.58(14) Te(1)–Mo(2)–Te(3) 91.25(6)
Te(2)–Mo(1)–S(2) 161.03(14) Te(4)–Mo(2)–Te(3) 115.25(7)
P(4)–Mo(1)–S(2)
Te(1)–Mo(1)–S(2)
S(1)–Mo(1)–S(2)
Te(2)–Mo(1)–Te(4) 108.98(7) O(8)–Mo(3)–Te(2) 168.0(3)
P(4)–Mo(1)–Te(4) 163.17(14) S(6)–Mo(3)–Te(2)
Te(1)–Mo(1)–Te(4) 107.41(6) S(5)–Mo(3)–Te(2)
S(1)–Mo(1)–Te(4)
S(2)–Mo(1)–Te(4)
O(7)–Mo(2)–S(3)
O(7)–Mo(2)–S(4)
S(3)–Mo(2)–S(4)
82.91(14) O(7)–Mo(2)–Te(3)
91.68(12) S(3)–Mo(2)–Te(3) 157.22(13)
84.3(2) S(4)–Mo(2)–Te(3) 81.76(13)
84.9(3)
i
˚
A in Mo3Te7[S2P(OPr )2]3I [16]. One m3-Te atom and three
m-Te atoms are located above and below the Mo3 plane,
respectively, to form an incomplete cuboidal clusterskeleton.
The Mo–(m-Te) distances range from 2.597(2) to 2.649(2)
A. The average Mo–(m3-Te) distance of 2.650 A is compa-
rable to those found in Mo3Te10I10 (2.661 A) [20],
[Mo3Te7(CN)6]3y (2.696 A) and [Mo4Te4(CN)12]
83.8(2)
88.99(13) O(8)–Mo(3)–S(5)
75.2(2) S(6)–Mo(3)–S(5)
O(8)–Mo(3)–S(6)
83.7(3)
82.8(3)
77.0(2)
˚
˚
˚
7y
˚
98.17(13)
86.11(13)
82.2(3)
y
˚
(2.676 A) [8–10]. In addition to the PhCO2 ligand that
bridges two Mo atoms and one PBu3 molecule coordinated
to the third Mo atom, there is a terminal S2P(OPri)2y ligand
chelating to each Mo atom. As a result, each Mo atom has a
distorted octahedral coordination geometry. The Mo–P dis-
82.17(13) O(8)–Mo(3)–Te(4)
83.13(14) S(6)–Mo(3)–Te(4)
81.93(14)
82.7(3)
83.5(3)
77.9(2)
S(5)–Mo(3)–Te(4) 155.27(14)
Te(2)–Mo(3)–Te(4) 109.73(7)
O(8)–Mo(3)–Te(3)
84.0(3)
˚
tance of 2.615(5) A is comparable to those of other com-
O(7)–Mo(2)–Te(1) 170.6(3)
S(6)–Mo(3)–Te(3) 157.8(2)
plexes containing the Mo3S4 cluster core and PPh3 ligand
[21,22].
In comparison, the structure of complex 2 is similar to that
of complex 1 with the (m3-Te) and bridging PhCO2y ligand
replaced by the (m3-S) and 2-aminobenzoic acid group. The
average Mo–Mo distance of 2 is slightly shorter (ca. 0.01–
S(3)–Mo(2)–Te(1)
S(4)–Mo(2)–Te(1)
O(7)–Mo(2)–Te(4)
S(3)–Mo(2)–Te(4)
97.94(13) S(5)–Mo(3)–Te(3) 83.23(14)
87.41(13) Te(2)–Mo(3)–Te(3) 90.28(6)
81.0(3)
Te(4)–Mo(3)–Te(3) 114.53(7)
81.58(12)
a Symmetry transformations usedtogenerate equivalentatoms:a1:yxy1/
2, yyy1/2, yzq1.
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X. Lin et al. / Polyhedron 19 (2000) 925–929
Fig. 1. Molecular drawings of (a) Mo3Te4[S2P(OPri)2]3(m-PhCO2)PBu3 (1) and (b) Mo3(m3-S)Te3[S2P(OPri)2]3(m-PhNH2CO2)PBu3 (2). The labels
for carbon and oxygen atoms have been omitted for clarity.
Fig. 2. ORTEP drawings of (a) Mo3Te4[S2P(OPri)2]3(m-PhCO2)PBu3 (1) and (b) Mo3(m3-S)Te3[S2P(OPri)2]3(m-PhNH2CO2)PBu3 (2) dimers showing
the atom labelling scheme at 30% probability of thermal ellipsoids. The butyl and isopropoxy groups have been omitted for clarity.
˚
0.05 A) than that of 1 because the capping sulfur atom has a
Mo–(m-Te) and the Mo–P distances are significantly elon-
gated (ca. 0.02–0.03 A for Mo–Te and 0.06 A for Mo–P).
˚
˚
smaller covalent radius than tellurium. On the other hand, the
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X. Lin et al. / Polyhedron 19 (2000) 925–929
929
Supplementary data
Crystallographic data have been deposited with the Cam-
bridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge, CB2 1EZ, UK (fax: q44-1223-336033; e-mail:
deposit@ccdc.cam.ac.uk) and are available on request quot-
ing the deposition numbers 135939 and 135940.
Acknowledgements
This research was supported by the National Natural Sci-
ence Foundation of China and the State Key Laboratory of
Structural Chemistry, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Sciences.
Fig. 3. 31P spectra of (a) Mo3Te4[S2P(OPri)2]3(m-PhCO2)PBu3 (1) and
(b) Mo3(m3-S)Te3[S2P(OPri)2]3(m-PhNH2CO2)PBu3 (2).
References
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It is interesting that there is a short contact between Te(3)
and Te(3A) of an adjacent molecule in both complexes
˚
˚
(3.103(2) A in 1 and 3.140(2) A in 2), leading to the
formation of a dimer (Fig. 2). Consequently, the distances
˚
of Te(3) and Mo are elongated (ca. 0.03–0.05 A) and the
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Sykes, J. Chem. Soc., Chem. Commun. (1998) 237.
[9] V.P. Fedin, I.V. Kalinina, D.G. Samsonenko, Y.V. Mironov, M.N.
Sokolov, S.V. Tkachev, A.V. Virovets, N.V. Podberezskaya, M.R.J.
Elsegood, W. Clegg, A.G. Sykes, Inorg. Chem. 38 (1999) 1956.
coordination environment of Te(3) is somewhat like that of
the m3-Te (the distances Te(3)–Mo are comparable with
Te(4)–Mo). EHMO calculation also attested that there is a
weak bond between two Te(3) atoms 1[23]. Although there
are some examples of longer Te∆Te interactions in existing
˚
tellurium-rich tellurides [24,25] (e.g. 3.07–3.17 A in LnTen
˚
´
[10] R. Hernandez-Molina, A. Geoffrey Sykes, J. Chem. Soc., Dalton
(n)1.75), 3.16 A in NaTe3), to our knowledge no example
of dimerization of two triangular Mo3E44q (EsS, Se) clus-
ters through bonding interaction has been found, although
the weaker dimerization through Se∆Se interaction (3.415
Trans. (1999) 1337.
[11] X. Xie, R.E. McCarley, Inorg. Chem. 35 (1996) 2713.
[12] A Muller, U. Reinsch, Angew. Chem., Int. Ed. Engl. 19 (1980) 72.
[13] V.P. Fedin, M.N. Sokolov, Y.V. Minronov, V.A. Kolesov, S.V.
Tkachev, V. Ye. Fedorov, Inorg. Chim. Acta 167 (1990) 39.
[14] V.P. Fedin, G.J. Lamprecht, T. Kohzuma, W. Clegg, M.J. Elsegood,
A.G. Sykes, J. Chem. Soc., Dalton Trans. (1997) 1747.
[15] M. Nasredlin, G. Henkal, G. Kampmanm, B. Kvebs, G.J. Lamprecht,
C.A. Routledge, A.G. Sykes, J. Chem. Soc., Dalton Trans. (1993)
737.
5y
˚
A) was reported in the [M3Se4(CN)9] (MsMo, W)
[14] anion before.
The 31P NMR spectra of complexes 1 and 2 are shown in
Fig. 3. The chemical shift of P1 of the DTP ligand is at 85.2
ppm for complex 1 (85.6 ppm for complex 2). The peak at
111.8 ppm for complex 1 (106.0 ppm for complex 2) with
twice integration can be assigned to P2 and P3 of the DTP
ligands, which coordinate symmetrically to Mo2 and Mo3,
and the chemical shift of PBu3 is at 22.3 ppm for complex 1
(17.8 ppm for complex 2). Compared to their counterparts,
dP1 has no significant shift and dP2, dP3 and dPBu3 for complex
2 have shifted to high field. The substitution of capping-Te
(in complex 1) by capping-S (in complex 2) in the cluster
core should be mainly responsible for these shifts.
[16] X. Lin, H.Y. Cheng, L.S. Chi, H.H. Zhuang, Polyhedron 18 (1999)
217.
[17] G.M. Sheldrick, SADABS, Absorption Correction Program, Univer-
¨
sity of Gottingen, Germany, 1996.
[18] Siemens, SHELXTLTM Version 5 Reference Manual, SiemensEnergy
& Automation Inc., Madison, WI, 1994.
[19] X. Lin et al., unpublished results, CCDC code 135941, 1999.
[20] V.P. Fedin, H. Imoto, T. Saito, J. Chem. Soc., Chem. Commun.
(1995) 1559.
[21] J.Q. Huang, S.F. Lu, Y.H. Lin, J.L. Huang, J.X. Lu, Acta Chim. Sinica
(1986) 301.
1 Molecular orbital reduced overlap populations (MP) between Te(3) and
Te(3A) are 0.052 for complex 1 and 0.027 for complex 2. The EHMO
calculations are based on the position of the atoms obtained from the X-ray
structure analysis. Standard atomic parameters of the program were used.
When we used a different atomic orbital parameter for tellurium (5s: y20.5,
2.57; 5p: y12.9, 2.16) [26], the MP between Te(3) and Te(3A) was 0.193
for complex 1 and 0.168 for complex 2.
[22] F.A. Cotton, P.A. Kibala, M. Matusz, C.S. McCaleb, B.W. Sandor,
Inorg. Chem. 28 (1989) 2623.
[23] C. Mealli, D.M. Proserpio, C.A.C.A.O., PC Version 4.0, J. Chem.
Educ. 67 (1990) 399.
[24] P. Bottcher, Angew. Chem., Int. Ed. Engl. 27 (1988) 759.
[25] M.G. Kanatzidis, Angew. Chem., Int. Ed. Engl. 34 (1995) 2109.
[26] X Xie, R.E. McCarley, Inorg. Chem. 36 (1997) 4665.
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