Intramolecular rearrangement behaviour of a dihydridoiridium (III)complex for med by regiospecific ‘chelate-assisted’ hydrosilylation

Abstract

Addition of PPh₂CH₂CH₂SiMe₂²H to [IrH(CO)](PPh₃)₃}is regiospecific as evidenced by formation of a cis adduct [I[graphic omitted]Me₂)(CO)(PPh₃)(H)(²H)]in which ²H nuclei are initially restricted to a single co-ordination position; subsequent rearrangement whereby ²H becomes equally distributed among the two hydridic sites is intramolecular with ΔG^‡₂₉₈= 19.3 ± 3.2kcal mol^–1(1kcal = 4.184kJ).