Cyclometalated iridium complexes based on monodentate aminophosphanes?

Dalton Transactions Pub Date: 2022-07-25 DOI: 10.1039/D2DT02081E

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 TOF1 min of about 2300 h?1 (5 mol% catalyst, 50 mol% sodium formate, DMF, 80 °C).

Graphical abstract: Cyclometalated iridium complexes based on monodentate aminophosphanes
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