- 作者: Amari Shingo ; Imoto Hideo ; Saito Taro
- 作者服務機構: Department of Chemistry, Faculty of Science, The University of Tokyo, Japan
- 中文摘要: Dodecanuclcar cluster complexes [Mo12S16(PEt3)10] 1 and [Mo12Se16(Pet3)10] 2 have been prepared by the reactions of [Mo6S8(PEt3)6] with sulfur or [Mo6Se8(PEt3)6] with Cp2TiSe5, respectively, in toluene at refluxing temperature. The structures have been determined at 173 K by X-ray crystallography. The compound 1.3CHCl3 crystallizes in the triclinic space group P1, with a = 14.859(5) A, b = 15.868(4) A, c = 14.200(7) A, α = 100.58(3)°, β = 117.58(3)°, γ = 79.53(2)°, V = 2899(1) A3, and Z=1. Full-matrix least-squares refinement using 9016 observed reflections (Io > 2σ(Io)) gave R = 0.056, and Rw = 0.045. The data for 2.2CHCl3 are: triclinic, P1, a = 15.737(4) A, b = 18.763(9) A, c = 13.062(4) A, α = 102.45(3)°, β = 128.54(2)°, γ=69.49(3)°, V = 2825 A3, Z = 1, R = 0.096, and Rw = 0.120 for 5922 reflections (Io > 2σ(Io)). The cluster complexes 1 and 2 have two octahedral molybdenum cluster units linked by the rhomboidal in-tercluster Mo2(μ4-E)2 bonding. The intercluster Mo---Mo distances in 1 are 3.419 A and 2 3.551 A. The cyclic voltammetry of 1 and 2 shows two oxidation and two reduction steps separated as large as 380-490 mV. The UV-Vis spectra of the dodecanuclear cluster complexes 1 and 2 have an extra weak band at around 744 nm which is absent in the starting octahedral cluster complexes.
- 英文摘要: --
- 中文關鍵字: Molybdenum Cluster; Chevrel Phase; Sulfide; Selenide; Triethylphosphine; Octahedral; Dodecannclear Cluster Complex
- 英文關鍵字: 鉬簇;晶籠相;硫化物;硒化物;三乙基膦;八面體;十二核簇錯合物