Synthesis of a Half-Sandwich Hydroxidoiridium(III) Complex Bearing a Nonprotic <i>N</i>-Sulfonyldiamine Ligand and Its Transformations Triggered by the Brønsted Basicity

Abstract

Synthesis and reactivities of a new mononuclear hydroxidoiridium(III) complex with a pentamethylcyclopentadienyl (Cp*) ligand are reported. The hydroxido ligand was introduced into an iridium complex having a nonprotic amine chelate derived from N-mesyl-N’,N’-dimethylethylenediamine by substitution of the chloride ligand using KOH. The resulting hydroxidoiridium complex was characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. The hydroxido complex was able to deprotonate benzamide and acetonitrile, and showed an ability to accept a hydride from 2-propanol to generate the corresponding hydrido complex quantitatively. In the reaction with mandelonitrile, a cyanide anion was transferred to the iridium center in preference to the hydride transfer. The cyanidoiridium complex was also identified in the reaction with acetone cyanohydrin, and could serve as catalyst species in the transfer hydrocyanation of benzaldehyde.

Keywords

• iridium
• hydroxido complex
• deprotonation
• hydride transfer
• cyanido complex
• transfer hydrocyanation
• amidato complex
• cyanomethyl complex