Angewandte Chemie - International Edition
Angewandte Chemie - International Edition
5 years ago

Oxidative P−P Bond Addition to Cobalt(−I): Formation of a Low-Spin Cobalt(III) Phosphanido Complex

Oxidative P−P Bond Addition to Cobalt(−I): Formation of a Low-Spin Cobalt(III) Phosphanido Complex
Christian Rödl, Serhiy Demeshko, Evamarie Hey-Hawkins, Robert Wolf, Peter Coburger
The first homoleptic cobalt phosphanido complex [K(thf)4][Co{1,2-(PtBu2)2C2B10H12}2] (1) was prepared by an unprecedented oxidative P−P bond addition of an ortho-carborane-substituted 1,2-diphosphetane to cobalt(−I) in [K(thf)0.2][Co(η4-cod)2)] (cod=1,5-cycloctadiene). Compound 1 is a rare distorted tetrahedral 3d6 complex with a low-spin ground state configuration. Magnetic measurements revealed that the complex is diamagnetic between 2 to 270 K in the solid state and at 298 K in [D8]THF solution. Based on DFT calculations, the unusual singlet ground state is caused by the strong σ-donor and moderate π-donor properties of the bis(phosphanido) ligand. Cobalt in a P pod: The first homoleptic cobalt phosphanido complex is formed via consecutive oxidative additions of P−P bonds to cobalt(−I). X-ray crystallography and magnetic measurements show that this new cobalt(III) compound is a rare example of a tetrahedral complex with a low-spin ground state.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201709140

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