Nucleophilic addition to the η6-iridathiabenzene ligand in [η6-Cp*Ir(C,S-2,5-Me2T)]FeCp+

The η6-iridathiabenzene ring coordinated to CpFe+ in [η6-Cp*Ir(C,S-2,5-Me2T)]FeCp+ (2) undergoes attack by nucleophiles. Phosphorus-donors, Ctriple bond; length of mdashN–Bun, and CN− add to the Ir to give products with an η5-coordinated iridathiabenzene ligand. Hydride (Et3BH−, View the MathML sourceHFe(CO)4-) and Ph− nucleophiles attack at the sulfur to give products with Ir–SH and Ir–SPh groups and an iridacyclopentadiene unit. Other reactions of 2 are described together with structure determinations of key compounds.