Preparation and Properties of the Full Series of Cuboidal Clusters [MoxW4-xSe4(H2O)12]n
详细信息 查看全文
- 作者：M. Sokolov ; P. Esparza ; R. Hernandez-Molina ; J. G. Platas ; A. Mederos ; J. A. Gavin ; R. Llusar ; and C. Vicent
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：February 21, 2005
- 年：2005
- 卷：44
- 期：4
- 页码：1132 - 1141
- 全文大小：265K
- 年卷期：v.44,no.4(February 21, 2005)
- ISSN：1520-510X
文摘
Hydrothermal reactions between incomplete cuboidal cluster aqua complexes [M3Q4(H2O)9]4+ and M(CO)6 (M =Mo, W; Q = S, Se) offer easy access to the corresponding cuboidal clusters M4Q4. The complete series of homometaland mixed Mo/W clusters [MoxW4-xQ4(H2O)12]n+ (x = 0-4, n = 4-6) has been prepared. Upon oxidation of themixed-metal clusters, it is the W atom which is lost, allowing selective preparation of new trinuclear clusters [Mo2WSe4(H2O)9]4+ and [MoW2Se4(H2O)9]4+. The aqua complexes were converted by ligand exchange reactions intodithiophosphato and thiocyanato complexes, and crystal structures of [W4S4((EtO)2PS2)6], [MoW3S4((EtO)2PS2)6],[Mo4Se4((EtO)2PS2)6], [W4Se4((i-PrO)2PS2)6], and (NH4)6[W4Se4(NCS)12]·4H2O were determined. Cyclic voltammetrywas performed on [MoxW4-xQ4(H2O)12]n+, showing reversible redox waves 6+/5+ and 5+/4+. The lower oxidationstates are more difficult to access as the number of W atoms increases. The [Mo2WSe4(H2O)9]4+ and [MoW2Se4(H2O)9]4+ species were derivatized into [Mo2WSe4(acac)3(py)3]+ and [MoW2Se4(acac)3(py)3]+, which were also studiedby CV. When appropriate, the products were also characterized by FAB-MS and NMR (31P, 1H) data.