An Experimental and Theoretical Study of the Structures and Properties of [CDPMe‐Ni(CO)3] and [Ni2(CO)4(µ2‐CO)(µ2‐CDPMe)

Abstract

The reaction of sym‐dimethyltetraphenyl carbodiphosphorane (CDPMe) with [Ni(CO)4] under standard conditions yields the CDPMe‐ and carbon monoxide‐bridged dinickel pentacarbonyl complex [Ni2(CO)4(µ2‐CO)(µ2‐CDPMe)] (2). However, under an atmosphere of CO(g), reaction of [Ni(CO)4] with CDPMe gives the primal target complex [CDPMe‐Ni(CO)3] (3). The complexes were examined in solution (ESI‐MS, NMR) and in the solid state (IR, X‐ray diffraction analysis). The resulting Tolman electronic parameter (TEP) and percentage buried volume value (%Vbur) of CDPMe are presented and compared with hexaphenyl carbodiphosphorane (CDPPh). DFT calculations were performed to analyze the bonding situation in complexes 2 and 3.