Synthesis and Structural Studies of Nickel(0) Tetracarbene Complexes with the Introduction of a New Four-Coordinate Geometric Index, τ_δ

Abstract

The synthesis and characterization of two homoleptic chelating nickel(0) tetracarbene complexes are reported. These are the first group 10 M(0) (M = Ni, Pd, Pt) tetracarbene complexes. These species have geometries intermediate between C2v sawhorse and tetrahedral and show high UV-vis absorption in the 350-600 nm range, with extinction coefficients (ϵ) between 5600 and 9400 M(-1) cm(-1). Density functional theory analysis indicates that this high absorptivity is due to metal-to-ligand charge transfer. In order to better describe the unusual geometries encountered in these complexes, an adjustment to the popular τ4 index for four-coordinate geometries is introduced in order to better delineate between sawhorse and distorted tetrahedral geometries.