C-Ni bond functionalization in the reaction of binuclear cyclometallated Ni(II) complexes with chlorophosphines

Abstract

This manuscript reports successful C-H nickellation of the aryl phosphinites (i-Pr2P(O-aryl) derived from un-substituted/substituted phenols: C6H5OH, 4-R-C6H4OH (R = F, MeO). Nickellation was observed with the phosphinites at an ortho-C-H position to generate Br-bridged dimers [{κP,κC-(i-Pr)2PO-aryl}cNi(μ-Br)]2 (C1-C3). While conversion of monomeric complexes from dimeric cyclonickellated complexes, functionalization behaviour was studied under inert atmosphere by reacting synthesized complexes with R2PX in various solvents. In order to understand the feasibility of the reaction and to evaluate the properties of product of insertion, phosphinite-phosphine nickel complexes were also approached from a second side. Appearance of specific signals in NMR spectra of products, provided strong evidences of formation of the target products exhibiting fluxional behaviour.

Keywords

• Functionalization
• Insertion
• Cyclonickellation
• Phosphinites