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A novel synthesis for dialkyl cobalt compounds [(tmeda)CoR2] is presented. In these complexes tmeda is readily replaced by an NHC or a bidentate phosphine ligand to form 3- and 4-coordinate compounds, respectively. [(ItBu)Co(CH2SiMe3)2] (ItBu = 1,3-di-tert-butylimidazolin-2-ylidene) serves as an efficient, homogeneous olefin hydrogenation pre-catalyst and allows the preparation of the novel cobalt bis(alkyne) complex [(ItBu)Co(η2-PhCCPh)2].

Graphical abstract: [(NHC)CoR2]: pre-catalysts for homogeneous olefin and alkyne hydrogenation

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