Reineke Mark H, Sampson Matthew D, Rheingold Arnold L, Kubiak Clifford P
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, Mail Code 0358, La Jolla, California 92093-0358, United States.
Inorg Chem. 2015 Apr 6;54(7):3211-7. doi: 10.1021/ic502792q. Epub 2015 Mar 10.
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.
报道了两种同配螯合四碳烯镍(0)配合物的合成与表征。这些是第一例第10族M(0)（M = Ni、Pd、Pt）四碳烯配合物。这些物种的几何形状介于C2v 锯架式和四面体之间，在350 - 600 nm范围内显示出高紫外可见吸收，消光系数（ϵ）在5600至9400 M(-1) cm(-1)之间。密度泛函理论分析表明，这种高吸收率是由于金属到配体的电荷转移。为了更好地描述这些配合物中遇到的异常几何形状，对用于四配位几何形状的常用τ4指数进行了调整，以便更好地区分锯架式和扭曲四面体几何形状。
