Cyclometalated iridium complexes based on monodentate aminophosphanes

Abstract

Monodentate aminophosphanes HNP [NH(4-tolyl)PPh₂] and SiMe₃NP [SiMe₃N(4-tolyl)PPh₂] react with [Ir(μ-Cl)(cod)]₂ affording tetra- or pentacoordinate complexes of formula [IrCl(L)_n(cod)] (L = HNP, n = 1, 2; L = SiMe₃NP, n = 1). The reaction of [IrCl(SiMe₃NP)(cod)] with carbon monoxide smoothly renders [Ir(CO)₃(SiMe₃NP)₂][IrCl₂(CO)₂]. The reaction of HNP or SiMe₃NP with [Ir(CH₃CN)₂(cod)][PF₆] yields the cyclometalated iridium(III)-hydride derivatives [IrH{κ²C,P-NR(4-C₆H₃CH₃)PPh₂}(cod)(CH₃CN)][PF₆] (R = H, SiMe₃) as a result of the intramolecular oxidative addition of the tolyl C²–H bond to iridium. The straighforward formation of [IrH{κ²C,P-SiMe₃N(4-C₆H₃CH₃)PPh₂}(cod)(CH₃CN)]⁺ was observed when the reaction was monitored by NMR spectroscopy at 233 K, whereas a more complex reaction sequence was observed in the formation of [IrH{κ²C,P-NH(4-C₆H₃CH₃)PPh₂}(cod)(CH₃CN)]⁺, including the formation of [IrH{κ²C,P-NH(4-C₆H₃CH₃)PPh₂}(HNP)(cod)]⁺ and [Ir(cod)(HNP)₂]⁺. The “mixed” complex [IrH{κ²C,P-SiMe₃N(4-C₆H₃CH₃)PPh₂}(HNP)(cod)]⁺ was obtained upon reaction of [IrH{κ²C,P-NH(4-C₆H₃CH₃)PPh₂}(cod)(CH₃CN)][PF₆] with SiMe₃NP at 233 K. Finally, the reaction of [Ir(CH₃CN)₂(coe)₂][PF₆] with SiMe₃NP or HNP resulted in the formation of [Ir(CH₃CN)₂(SiMe₃NP)₂][PF₆] and [IrH{κ²C,P-NH(4-C₆H₃CH₃)PPh₂}(HNP)₂(CH₃CN)][PF₆], respectively. Both the OC-6-35 and the OC-6-52 isomers of [IrH{κ²C,P-NH(4-C₆H₃CH₃)PPh₂}(HNP)₂(CH₃CN)]⁺ – featuring facial and meridional dispositions of the phosphorus atoms, respectively – were isolated depending on the reaction solvent. Several compounds described herein catalyse the dehydrogenation of formic acid in DMF, [IrCl(HNP)₂(cod)] being the most active, with TOF_{1 min} of about 2300 h⁻¹ (5 mol% catalyst, 50 mol% sodium formate, DMF, 80 °C).