Coordinately unsaturated XCo(CO)3 (X = H, SiR3) species are of particular interest because of their relevance to hydroformylation and hydrosilylation catalysis, as well as their small molecule activation abilities. However, to date, these coordinatively unsaturated carbonyl species remain unisolable. Presented are the unique reactivity of the isolable isocyanide analogue (SiMe3)Co(CNArMes2)3 (ArMes2 = bis–(2,4,6–Me3–C6H2)-C6H3). Based on its trigonal-pyramidal geometry observed in the solid state, the electronic structure is ideally suitedfor binding weak Lewis bases due to the high-lying Co-Si σ*-orbital with predominantly Co-dz2 character. A variety of Lewis acid-base adduct (L)Co(SiMe3)(CNArMes2)3 were made including L = N2, CO, DME and H2O. Importantly, reaction of (SiMe3)Co(CNArMes2)3 with nitrous oxide (N2O), a substrate that is well-known to serve as a poor ligand for transition metals, afforded was able to form the k1-N-N2O complex, (k1-N-N2O)Co(SiMe3)(CNArMes2)3,, which has been structurally characterized. The decomposition of (k1-N-N2O)Co(SiMe3)(CNArMes2)3 leads to cleanly OCNArMes2 and (N2)Co(SiMe3)(CNArMes2)3, indicating that the complex can engage in O-atom transfer processes. The mechanism of this and other reactions of (k1-N-N2O)Co(SiMe3)(CNArMes2)3 are discussed.

N2O binding on RCo(CNR)3 and O-atom transfer reactions

255th National Meeting (2018)

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