An investigation of the reactivity of [(diimine)(dithiolato)M] complexes using the Fukui functions concept

作者：Makedonas C; Mitsopoulou CA^*

来源：European Journal of Inorganic Chemistry, 2006, 2006(3): 590-598.

DOI：10.1002/ejic.200500664

• density functional calculations
• Fukui indices
• oxidation
• S ligands
• Schiff bases
• stacking interactions

Fukui functions are widely used when investigating the reactivity of organic molecules, but rarely with metal complexes. Here, we investigate the reactivity of [(diimine)(dithiolato)M] complexes with different types of reagents and upon oxidation employing this concept. Mixed-ligand complexes of this type have a peculiar electronic description due to the mixed-metal-ligand-to-ligand charge-transfer band, which is why they are considered as very promising candidates for non-linear optical (NLO) materials and molecular photochemical devices (MPD). As a result, their reactivity is of crucial importance for their potential applications. The obtained results of f(+) and f(-) for the neutral [(diimine)(dithiolato)M] complexes (M = Pd, Ni and Pt) not only predict that the sulfur atom is the preferable active site for electrophilic attack but also reveal the different tunability of these complexes when they are subjected to an oxidation process, in agreement with experimental results. Under the framework of the Fukui indices we also provide an alternative explanation for crystal packing that could find widespread application.

• 出版日期2006-2-6