Novel Families of Three-Component Reversible Redox Cycles Involving Cage Deformation via Intramolecular Redox Reaction: Tetrathiolate-Bridged Dinuclear Molybda- and Tungstacarboranes
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- 作者：Jeong-Wook Hwang ; Jae-Hak Kim ; Hangil Lee ; Hochun Lee ; Sehun Kim ; Juhyoun Kwak ; and Youngkyu Do
- 刊名：Journal of the American Chemical Society
- 出版年：2001
- 出版时间：September 19, 2001
- 年：2001
- 卷：123
- 期：37
- 页码：9054 - 9063
- 全文大小：168K
- 年卷期：v.123,no.37(September 19, 2001)
- ISSN：1520-5126
文摘
The synthesis and structural analysis of two novel families of three-component reversible redoxcycles [(C2B9H11)M(
-SPh)2]2nPPNn (M = Mo, n = 2-, 2; 1-, 3; 0, 4; and M = W, n = 2-, 6; 1-, 7; 0, 8),where the cleavage and re-formation of the carborane cage C-C bond is observed during the redox reaction,are reported. Electronic saturation of the metal center (18e center) and the lack of bulky substituents on thecarborane cage suggest that the deformed carborane cages in 2·PPN2, 6·PPN2, and 7·PPN invoke a new kindof deformed cage ("semicloso" framework). The XPS results show that the unprecedented competition forelectron density between the metal center and the carborane cage is involved in the cleavage and formation ofthe carborane C-C bond.
-SPh)2]2nPPNn (M = Mo, n = 2-, 2; 1-, 3; 0, 4; and M = W, n = 2-, 6; 1-, 7; 0, 8),where the cleavage and re-formation of the carborane cage C-C bond is observed during the redox reaction,are reported. Electronic saturation of the metal center (18e center) and the lack of bulky substituents on thecarborane cage suggest that the deformed carborane cages in 2·PPN2, 6·PPN2, and 7·PPN invoke a new kindof deformed cage ("semicloso" framework). The XPS results show that the unprecedented competition forelectron density between the metal center and the carborane cage is involved in the cleavage and formation ofthe carborane C-C bond.