[Ni(OMe)]-mediated reductive activation of CO affording a Ni(κ-OCO) complex.

Carbon dioxide is expected to be employed as an inexpensive and potential feedstock of C sources for the mass production of valuable chemicals and fuel. Versatile chemical transformations of CO, insertion of CO producing bicarbonate/acetate/formate, cleavage of CO yielding μ-CO/μ-oxo transition-metal complexes, and electrocatalytic reduction of CO affording CO/HCOOH/CHOH/CH/CH/oxalate were well documented. Herein, we report a novel pathway for the reductive activation of CO by the [Ni(OMe)(P(CH-3-SiMe-2-S))] complex, yielding the [Ni(κ-OCO˙)(P(CH-3-SiMe-2-S))] complex.

Formation of [Ni(III)(κ(1)-S2CH)(P(o-C6H3-3-SiMe3-2-S)3)]- via CS2 insertion into nickel(III) hydride containing [Ni(III)(H)(P(o-C6H3-3-SiMe3-2-S)3)]-.

Insertion of CS2 into the thermally unstable nickel(III) hydride [PPN][Ni(H)(P(o-C6H3-3-SiMe3-2-S)3)] (1), freshly prepared from the reaction of [PPN][Ni(OC6H5)P(C6H3-3-SiMe3-2-S)3] and 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (HBpin; pin = OCMe2CMe2O) in tetrahydrofuran at -80 °C via a metathesis reaction, readily affords [PPN][Ni(III)(κ(1)-S2CH)(P(o-C6H3-3-SiMe3-2-S)3)] (2) featuring a κ(1)-S2CH moiety.