Cleavage of Carbon Monoxide Promoted by a Dinuclear Tantalum Tetrahydride Complex

Abstract

The reaction of one equivalent of carbon monoxide with the dinuclear tetrahydride complex ([NPN]Ta) 2 (μ-H) 4 (where NPN = PhP(CH 2 SiMe 2 NPh) 2 ) results in the cleavage of the CO triple bond and formation of ([NPN]Ta)(μ-O)(μ-H)(Ta[NPN′]) (where NPN′ = PhP(CH 2 SiMe 2 NPh)(CH 2 SiMe 2 NC 6 H 4 )) via extrusion of CH 4 . The identity of the ditantalum complex was confirmed by single-crystal X-ray analysis, isotopic labeling studies, and GC-MS analysis of the methane released. DFT calculations were performed to provide information on the initial adduct formed and likely transition states for the process.