The synthesis and crystal structures of the first species of monocubane type clusters [Mo 3PbS 4] 6+ and [Mo 3BiS 4] 7

• Published in: Inorganica Chimica Acta 1997-09, Vol.261 (2), p.201-209
• Main Authors: Lu, Shao-Fang, Huang, Jian-Quan, Wu, Qiang-Jin, Huang, Xiao-Ying, Yu, Rong-Min, Zheng, Yu, Wu, Da-Xu
• Format: Article
• Language: English
• Subjects: Bismuth complexes; Cluster complexes; Crystal structures; Electron transfer; Lead complexes; Molybdenum complexes
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(97)05475-3

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) 2CO( II) (dtp=S 2P(OC 2H 5) 2 −;OAc=(OOCCH 3) −) are reported. They resulted from the reaction of trinuclear Mo 3S 4(dtp) 4·H 2O with PbI 3 − and BiI 3, respectively. Both of the molecular structures have an [Mo 3MS 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 95Mo NMR spectrum before and after the addition reaction. Crystal data: I: triclinic, Pl̄, a = 11.087(2), b = 12.760(5), c = 19.358(4), Å, α = 94.37(3), β = 92.39(2), γ = 99.46(2)°, V = 2689(2), Å 3, Z = 2. Least-squares refinement of 4462 reflections gave a final agreement factor of R = 0.052 ( Rw = 0.058); II: triclinic, Pl̄, a = 11.696(4), b = 13.044(4), c = 18.241(6), Å, α = 74.90(3), β = 75.96(3), γ = 88.06(3)°, V = 2605(3)Å 3, Z = 2. Least-squares refinement of 5913 reflectioins gave a final agreement factor of R = 0.054 ( Rw = 0.061).