ChemInform Abstract: Electronic Structures of (M3(μ3-X)(μ2-S2)3)4+ (M: Mo, Ti) Cluster Compounds and the Effects of the μ3-X Cap to the Self- Assembly in Cluster Synthesis.

Abstract

Abstract The electronic structures and bonding in one class of trinuclear transition-metal cluster compounds having the cores [Ti3(μ3-O)(μ2-S2)3]4+ (1), [Mo3(μ3-S2)3]4+ (2) and [MO3S4]4+ (3) are discussed in terms of the results of molecular orbital (MO) calculations using the CNDO/ 2-LMO method. There are certain strong bonding interactions between the metal atoms in clusters 2 and 3, but no significant metal-metal bonding is found in cluster 1. The existence of one four-centred bond consisting of three skeletal Mo atoms and the μ3 cap in cluster 2 is of particular importance for shedding light on the nature of the self-assembly syntheses. From the analysis of the localized MO (LMO) we conclude that the μ3-O cap and the μ3-S cap have an important effect on the self-assembly of the trinuclear clusters.