The electronic structure of the dizincocene core

Abstract

Ab initio plane wave based density functional theory calculations were used to examine the properties of the dimetal core of the recently synthesised dizincocene Zn 2(η 5-C 5Me 5) 2. Neutral Zn 2 and the zincous dication Zn 2 2 + were the primary targets and copper dimer Cu 2, iron dimer Fe 2 and the simpler model dizincocene Zn 2(η 5-C 5H 5) 2 were examined for comparisons. The zincous ion has features arising from mixing of s-, p-, and d-functions that appear in the isoelectronic copper Cu 2 ( S = 0) dimer, iron Fe 2 ( S = 0) dimer and the dizincocene molecule. Isometric surfaces of the total charge, Kohn–Sham level partial charge density and the electron localization function (ELF) are reported. The metal–metal valence basin of the ELF density comprised toroidal and axial components, a motif common to the copper and iron dimers and dizincocene. These results are important for understanding the structure of the known and hypothetical dimetallocenes of the first transition series.