Germylene stabilized group 12 metal complexes and their reactivity with chalcogens

Abstract

This manuscript reports the first examples of germylene stabilized cadmium complexes {[{(i-Bu)₂ATIGe(i-Pr)}₂(CdI₂)] (3, monomeric), [{(i-Bu)₂ATIGe(i-Pr)(CdCl₂)}₂] (6, dimeric), [{(i-Bu)₂ATIGe(i-Pr)(CdI₂)}₂] (7, dimeric)} and novel germylene zinc complexes {[{(i-Bu)₂ATIGe(i-Pr)}₂(ZnCl₂)] (2, monomeric), [{(i-Bu)₂ATIGe(i-Pr)(ZnI₂)}₂] (5, dimeric)} (ATI = aminotroponiminate). The reactions of germylene zinc complex [{(i-Bu)₂ATIGe(i-Pr)(ZnCl₂)}₂] (4) with elemental sulphur and selenium resulted in the first examples of germathione and germaselenone stabilized ZnCl₂ complexes [{(i-Bu)₂ATIGe(i-Pr)(S)(ZnCl₂)}₂] (8) and [{(i-Bu)₂ATIGe(i-Pr)(Se)(ZnCl₂)}₂] (9), respectively. Compound 4 was obtained through the reaction of compound 2 with ZnCl₂. Interconversions between the monomeric and dimeric zinc/cadmium complexes (2 ↔ 4/3 ↔ 7) are shown. Compounds 2–3 and 5–9 are characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction studies are performed on compounds 2–3, 5–7, and 9. To understand the nature of bonding in the first examples of germylene cadmium complexes, ab initio calculations are also carried out on compounds 3 and 7.