The sterically encumbering m-terphenyl isocyanide, CNArMes2 (Mes = 2,4,6-Me3C6H2), has been used as a chemical surrogate for CO in the attempts of stabilizing highly reduced organometallic species. Presented here is the synthesis, spectroscopic characterization, and electronic structure analysis of a series of cobalt dimers with the general formulation [(?5-Cp)2Co2(�2-CNArMes2)2]n (where n = 0, -1, -2). These complexes are isocyanide analogs to the previously reported (?5-Cp)Co- carbonyl dimers. However, a discontinuity arises when compared to this previous CO series; the use of m-terphenyl isocyanides allows for the isolation of dimers spanning (d8-d8)-(d9-d9) electronic configuration previously unheard of for a (?5-Cp)2Co2(�2-L)2 systems. In addition, presented here is the isolation of K2[(?5-Cp)2Co2(�-CNArMes2)2], an analogue to the elusive carbonyl dianion [(?5-Cp)2Co2(�-CO)2]2�. Computational and reactivity studies demonstrate that [(?5-Cp)2Co2(�-CO)2]2� can be considered as an isolobal variant to the bridging-carbonyl, C2v-symmetric form of Co2(CO)8.

Cobalt dimers stabilized by m-terphenyl isocyanides: Analogs to [(CpCoCO)<sub>2</sub>]<sup>n </sup>(n=0,-1,-2) in three states of charge

248th National Meeting (2014)

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Cobalt dimers stabilized by m-terphenyl isocyanides: Analogs to [(CpCoCO)2]n (n=0,-1,-2) in three states of charge

Cobalt dimers stabilized by m-terphenyl isocyanides: Analogs to [(CpCoCO)₂]ⁿ(n=0,-1,-2) in three states of charge