Structures of dimetallocenes M₂(C₅H₅)₂ (M = Zn, Cu, Ni, Co, Fe) and their perfluorinated derivatives

Abstract

Density functional theory shows that the dizincocenes Zn2(C5X5)2 (X = H, F) have singlet coaxial structures with two (η5-C5X5)Zn units linked by a Zn–Zn single bond. However, the low-energy M2(C5H5)2 (M = Cu–Fe) structures have perpendicular configurations with bridging C5H5 ligands.

All‐Metallic Zn=Zn Double‐π Bonded Octahedral Zn2M4 (M=Li, Na) Clusters with Negative Oxidation State of Zinc

“…Since then, the study of ZnÀ Zn chemical bond has attracted wide attention and ZnÀ Zn bonded compounds have given rise to an ever-growing family. [14,[21][22][23][24] Among these ZnÀ Zn bonded complexes, the researchers almost invariably adopt terminal ligands to bind the σ antibonding electrons and to construct a ZnÀ Zn bond. Nevertheless, there is only one study discussed theoretically about the ZnÀ Zn multiple bond reported by Echeverría et.al.…”

“…The electrons of σ antibonding orbital in original Zn 2 fragment are bound by the organic ligands at both Zn−Zn ends and hence a Zn−Zn single bond is formed with a +1 oxidation state. Since then, the study of Zn−Zn chemical bond has attracted wide attention and Zn−Zn bonded compounds have given rise to an ever‐growing family . Among these Zn−Zn bonded complexes, the researchers almost invariably adopt terminal ligands to bind the σ antibonding electrons and to construct a Zn−Zn bond.…”