Jian-Quan Huang

The synthesis and crystal structures of the first species of monocubane type clusters [Mo3PbS4]6+ and [Mo3BiS4]7+

The synthesis and crystal structure of two heteronuclear transition metal-main group metal cubane-like cluster compounds [Mo 3 (PbI 3 )S 4 (dtp) 3 (py) 3 ] ( I ) and [Mo 3 (BiI 3 )S 4 (μ-OAc)(dtp) 3 ·(py)]·(CH 3 ) 2 CO( II ) (dtp=S 2 P(OC 2 H 5 ) 2 − ;OAc=(OOCCH 3 ) − ) are reported. They resulted from the reaction of trinuclear Mo 3 S 4 (dtp) 4 ·H 2 O with PbI 3 − and BiI 3 , respectively. Both of the molecular structures have an [Mo 3 MS 4 ] core (MPb, Bi) but their molecular configurations are different. The electron transfer of a lone pair electrons of M metals occurs in the additive clusters I and II , thus enhancing the MoMo bonding. Evidence for this is seen in the 95 Mo NMR spectrum before and after the addition reaction. Crystal data: I : triclinic, P l, a = 11.087(2), b = 12.760(5), c = 19.358(4), A, α = 94.37(3), β = 92.39(2), γ = 99.46(2)°, V = 2689(2), A 3 , Z = 2. Least-squares refinement of 4462 reflections gave a final agreement factor of R = 0.052 ( Rw = 0.058); II : triclinic, P l, a = 11.696(4), b = 13.044(4), c = 18.241(6), A, α = 74.90(3), β = 75.96(3), γ = 88.06(3)°, V = 2605(3)A 3 , Z = 2. Least-squares refinement of 5913 reflectioins gave a final agreement factor of R = 0.054 ( Rw = 0.061).

Synthesis and structural characterization of hybrid Group 12, 14, 15 metals-molybdenum (tungsten) cluster compounds

For the heterometallic cluster compounds containing a core of [M3YS3M] (4 + n)+ (M= Mo, W; Y= O, S; M= metal atom except Mo, W), a relatively comprehensive understanding has already been made when M n + appears to be a transition metal. When M n + is a main group metal, however, what will be the situation? This certainly arouses the interest among the chemists. In this present work, the synthesis, new reaction types, crystal structures and spectroscopic characterization of a series of 33 hybrid Mo(W)–Group 12, 14, 15 metal clusters are summarized. These crystals can be put into three categories, i.e. the single cubane type which contains a [M3YS3M ]c ore (M=Mo, W; Y= O, S; M= Sn, Pb, Sb, Bi) (SC type), the double cubane clusters coupled by two bridging oxygen atoms possessing a [Mo3OS3M (-O)]2 core (M= Pb, Bi) (DC type) and the ionic clusters (IO type) which consists of a {Mo3} cluster cation and a M complex anion (M= Cd, Hg). It is shown that the incorporation of the main group metal M is through MS bonding between M and three (-S) atoms of the [M3YS3] cluster core, similar to the case when M is a transition metal atom. The bonding is however comparatively looser than in the case of a transition metal. The synthetic reactions and structural features of these clusters are discussed. Furthermore, information on the third-order nonlinear optical property observed in some of these compounds is reported.

Ligand-cluster reactivity and structure relationship; the synthesis, structural characterization and properties of two new MoCuS cluster compounds

By using Mo3S4(dtp)4·H2O (dtp = S2P(OEt)2) as starting material and from the substitution reaction of ligands and the addition reaction with CuI, two novel MoCuS cubane-like cluster compounds {[CuMo3S4]·I·(μ-dtc)(dtc)3·py}· CH3COOC2H5 (5) and {[CuMo3S3X·I·(O)2(dtcpyr)3dpy}(CH3COOC2H5)0.6(H2O)0.4 (6) (X34O+ 14S, dtc + S2CN(Et)2, dtcpyr = S2CN(C4H8)) have been obtained. The synthesis, structural characterization and properties of these two clusters as well as their comparison with dtp structural analogues are described. The ligand—cluster reactivity and structure relationship is also discussed. Crystal data: for 5 space group P1 a = 16.22358(6), b = 16.220(9), c = 11.421(5) →A, α = 104.004(4), β = 110.54(4), ψ = 87.23(5)°, Z = 2,4809 reflections, R = 0.041; for 6; space group P21/n, a = 15.179(9), b = 16.353(6), c = 17.621(9) A, β = 112.18(5)°, Z = 4, 3469 reflections, R = 0.047.

Synthesis, crystal structure and bonding features of a trinuclear cluster [Mo3X(S2)3(dtp)3I3] (X=O,S) with layer-like packing

Abstract The reaction of Mo 3 OS 3 (dtp) 4 (H 2 O) (dtp=S 2 P(OC 2 H 5 ) 2 ) with CuI yielded the new trimolybdenum cluster [Mo 3 (μ 3 -X)(μ 2 -S 2 ) 3 (dtp) 3 I 3 ] (X=58%O+42%S). Crystal structure analysis showed that the compound has a [Mo 3 X(S 2 ) 3 ] 4+ cluster core, and the I 3 − group functions as a two-way coordinated ligand which links the three out-of-{Mo 3 } plane S atoms in the cluster core at one end (I–S∼3.3 A) and two adjacent trinuclear clusters at the other (I⋯S∼3.6 A), thus forming a [Mo 3 X(S 2 ) 3 ] cluster layer. The bonding features of the cluster characteristic of a semiconductor are demonstrated by energy band and density functional calculations.

The synthesis and structural characterization of a novel Bi–Mo double cubane cluster coupled by two bridging oxygen atoms { [Mo3 (BiI3)OS3 (μ-OAc)2 (py)3]2 (μ-O)2}·2 (H2O)

Abstract With [Mo3 (μ3-O) (μ-S)3 (μ-OAc)2 (dtp)2 (py)] (dtp=S2P(OC2H5)2)−; OAc=OOCCH −3; py=C5H5N) as the starting material, the reaction together with BiI3 in presence of (H2O) results in a novel Bi–Mo double-cubane cluster coupled by two bridging oxygen atoms { [Mo3 (BiI3) (μ3-O) (μ3-S)3 (μ-OAc)2 (py)3]2 (μ-O)2}·2 (H2O) 2. The cluster 2 has been characterized by IR, Raman, UV–Vis, NMR and single-crystal X-ray study. A comparison is made between these results and those of the previously reported single cubane Bi–Mo cluster [Mo3 (BiI3) (μ3-S)4 (μ-OAc) (dtp)3 (py)] 1.

Synthesis, structural characterization and bonding properties of heterometallic-heterobridging cubane-type tetranuclear cluster compounds [CuMo3OS3]·I·(μ-OAc)[S2P(OC2H5)2]3·L (L=py, DMF)

AbstractBy the reaction of cluster [Mo3OS3](dtp)4(H2O) used as starting material with CuI using [3+1] mode, two novel heterometallic-heterobridging cubane-type tetranuclear cluster compounds [CuMo3OS3]·I·(μ-OAc)[S2P(OC2H5)2]3·L [(I)L=py, (II)L=DMF] [dtp=S2P(OC2H5)2; OAc=OOCCH3] containing [CuMo3OS3] core have been obtained. Compounds (I) and (II) have been characterized by IR, EPR, UV-VIS, electrochemistry and X-ray crystallography. By comparison of these two compounds with the analogous [CuMo3S4] series in the structure and molecular orbital calculation, the influence of mixed S/O bridging on the structure is discussed. It is demonstrated that the {Mo3S3} cluster ring in [Mo3OS3]4+ possesses a similar quasi-aromaticity to [Mo3S4]4+. Crystal data: for (I), space group=

The synthesis and crystal structure of a trinuclear molybdenum cluster compound [Mo3(μ‐O)(μ‐S)3(μ(μ‐OAc)2(dtp)2·(Py)]·0.5H2O

P\overline 1

A Novel Nickel-Containing Chain-Like Polymer: ({Ni(NH3)4}Ni{S2C~C(CN)2}2)~

,a=13.781(8)Å,b=14.523(6)Å,c=12.098(6)Å, α=98.37(4)°, β=109.41(5)°, γ=105.00(5)°,V=2133(2)Å3,Z=2,R=0.058; for (II), space group=