Novel families of three-component reversible redox cycles involving cage deformation via intramolecular redox reaction: Tetrathiolate-bridged dinuclear molybda- and tungstacarboranes
- Authors
- 황정욱; 김재학; 이한길; 이호춘; 김세훈; 곽주현; 도영규
- Issue Date
- Sep-2001
- Publisher
- ACS
- Citation
- Journal of the American Chemical Society, v.123, no.37, pp 9054 - 9603
- Pages
- 550
- Journal Title
- Journal of the American Chemical Society
- Volume
- 123
- Number
- 37
- Start Page
- 9054
- End Page
- 9603
- URI
- https://scholarworks.sookmyung.ac.kr/handle/2020.sw.sookmyung/149528
- DOI
- 10.1021/ja0106265
- ISSN
- 0002-7863
1520-5126
- Abstract
- The synthesis and structural analysis of two novel families of three-component reversible redox cycles [(C2B9H11)M(μ-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 the carborane cage suggest that the deformed carborane cages in 2·PPN2, 6·PPN2, and 7·PPN invoke a new kind of deformed cage (“semicloso” framework). The XPS results show that the unprecedented competition for electron density between the metal center and the carborane cage is involved in the cleavage and formation of the carborane C−C bond.
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