The synthesis, solution dynamics and reaction chemistry of zwitterionic complex [?2-PPN][Co(CNArMes2)3] (1  ) is presented (ArMes2 = 2,6-(2,4,6-Me3C6H2)2C6H3; PPN = [Ph3PNPPh3]+). Zwitterion 1  functions as a source of the coordinatively unsaturated, 16 e-� trisisocyanometalate, [Co(CNArMes2)3]�, by virtue of a labile ?2-phenyl interaction between the Co center and the PPN+cation. Treatment of zwitterion 1  with main group electrophiles generates four-coordinate complexes of formulation XCo(CNArMes2)3. Newly installed X ligands possessing only s-donating properties allow the Co center to retain coordinative unsaturation and the ensuing complexes are active in a range of additional small molecule binding and activation reactions. Reactions between zwitterion 1  and organic electrophiles are also presented. A highlight of this reaction chemistry is a novel CO for NCR exchange process within the ring of cyclic carbonyl anhydrides.

Bond activation and substrate binding by low-coordinate cobalt isocyanides

245th National Meeting (2013)

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