Iridium(III) bis(thiophosphinite) pincer complexes: synthesis, ligand activation and applications in catalysis

Iridium(III) bis(thiophosphinite) complexes of the type [(^RPSCSP^R)Ir(H)(Cl)(py)] (^RPSCSP^R = κ³-(2,6-SPR₂)C₆H₃) (R = tBu, iPr, Ph) can be prepared from the ligand precursors 1,3-(SPR₂)C₆H₄ by C-H activation at Ir using [Ir(COE)₂Cl]₂ or [Ir(COD)Cl]₂. Optimisation of the protocol for complexation showed that direct cyclometallation in the absence or presence of pyridine, as well as C-H activation in the presence of H₂ are viable options that, depending on the phosphine substituent furnish the five-coordinate Ir(III) hydride chloride complexes 2-R or the base stabilised species 3-R in good yields. In case of the ^PhPSCSP^Ph ligand, P-S activation results in the formation of a thiophosphine stabilised Ir(III) hydride complex [(^PhPSCSP^Ph)Ir(H)(Cl)(PPh₂SH)] (4). Reaction of 2-tBu with H₂ in the presence of base furnishes an Ir(III) dihydride complex (5) via a labile Ir(III) dihydride-dihydrogen complex (6). All complexes are inactive for transfer dehydrogenation of cyclooctane in the presence of NaOtBu and tert-butylethylene, likely due to decomposition of the Ir complex in the presence of base at higher temperature.