Redox-Switched Oxidation of Dihydrogen Using a Non-Innocent Ligand

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• 作者：Mark R. Ringenberg ; Swarna Latha Kokatam ; Zachariah M. Heiden ; Thomas B. Rauchfuss
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：January 23, 2008
• 年：2008
• 卷：130
• 期：3
• 页码：788 - 789
• 全文大小：81K
• 年卷期：v.130,no.3(January 23, 2008)
• ISSN：1520-5126

文摘

Organometallic complexes containing non-innocent ligands of the type Cp*Ir(^tBA^FPh)(1), where H₂^tBA^FPh is 2-(2-trifluoromethyl)anilino-4,6-di-tert-butylphenol, were found to activate H₂ in a redox-switchable manner. The 16e^- complex 1 was inert with respect to H₂, CO, as well as conventional basic substrates until oxidation. Oxidation of 16-electron 1 with 1 equiv of Ag⁺ resulted in ligand-centered oxidation affording salts of [1]⁺, which were characterized by crystallographically, EPR, and elemental analyses. [1]⁺ was reduced to 1 in the presence of H₂ and the sterically hindered base, 2,6-(^tBu)₂C₅H₃N, via a pathway that is first-order in both metal and dihydrogen. Compound [1]⁺ forms adducts with MeCN, which inhibits catalysis. The catalytic oxidation of H₂ was established by electrochemical methods to be associated with the monocation.