Metal鈥揗etal Bonding in Low-Coordinate Dicobalt Complexes Supported by Phosphinoamide Ligands

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• 作者：Ramyaa Mathialagan ; Subramaniam Kuppuswamy ; Alexandra T. De Denko ; Mark W. Bezpalko ; Bruce M. Foxman ; Christine M. Thomas
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：January 18, 2013
• 年：2013
• 卷：52
• 期：2
• 页码：701-706
• 全文大小：366K
• 年卷期：v.52,no.2(January 18, 2013)
• ISSN：1520-510X

文摘

Homobimetallic dicobalt complexes featuring metal centers in different coordination environments have been synthesized, and their multielectron redox chemistry has been investigated. Treatment of CoX₂ with MesNKPⁱPr₂ leads to self-assembly of [(THF)Co(MesNPⁱPr₂)₂(渭-X)CoX] [X = Cl (1), I (2)], with one Co center bound to two amide donors and the other bound to two phosphine donors. Upon two-electron reduction, a ligand rearrangement occurs to generate the symmetric species (PMe₃)Co(MesNPⁱPr₂)₂Co(PMe₃) (3), where each Co has an identical mixed P/N donor set. One-electron oxidation of 3 to generate a mixed valence species promotes a ligand reararrangement back to an asymmetric configuration in [(THF)Co(MesNPⁱPr₂)₂Co(PMe₃)][PF₆] (4). Complexes 1鈥?b>4 have been structurally characterized, and their metal鈥搈etal interactions are discussed in the context of computational results.