Aryl group transfer and C–P bond formation in the reaction of organonickel complexes with sodium 3,4,5-triphenyl-1,2-diphospholide

Abstract

The reaction of organonickel complexes of the type [NiBr(aryl)(bpy)], where aryl = 2,4,6-trimethylphenyl (Mes, 1), 2,3,4,5,6-pentamethylphenyl (Pmp, 2), 2,4,6-triisopropylphenyl (Tipp, 3), bpy = 2,2′-bipyridine, with sodium bis(diglyme) 3,4,5-triphenyl-1,2-diphosphacyclopentadienide (sodium 1,2-diphospholide, SDP) leads to unknown 1-aryl-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-dienes (1-aryl-1,2-diphospholes, ADPs) 4-6 by the organic group transfer from organonickel complexes to 3,4,5-triphenyl-1,2-diphospholide (DP). The mechanism of the reaction was explored by experimental (ESI-MS, ESR spectroscopy) and quantum-chemical (DFT) methods suggesting the formation of intermediate nickel(II) phospholide complexes capable of reductive elimination leading to the desired organophosphorus products and nickel nanoparticles (NiNPs). The solid-state luminescence of the obtained 1-aryl-3,4,5-triphenyl-1,2-diphospholes 4-6 was investigated.