Synthesis and reactivity of an iridium complex based on a tridentate aminophosphano ligand

Abstract

The iridium(III) hydride compound [IrH{κ³C,P,P′-(SiNP–H)}(CN^tBu)₂][PF₆] (1PF₆) was obtained by reaction of [Ir(SiNP)(cod)][PF₆] with CN^tBu as the result of the intramolecular oxidative addition of the SiCH₂–H bond to iridium(I) [SiNP = Si(CH₃)₂{N(4-tolyl)PPh₂}₂, SiNP–H = CH₂Si(CH₃){N(4-tolyl)PPh₂}₂]. The mechanism of the reaction was investigated by NMR spectroscopy and DFT calculations showing that the pentacoordinated intermediate [Ir(SiNP)(cod)(CN^tBu)][PF₆] (2PF₆) forms in the first place and that further reacts with CN^tBu, affording the square planar intermediate [Ir(SiNP)(CN^tBu)₂][PF₆] (3PF₆) that finally undergoes the intramolecular oxidative addition of the SiCH₂–H bond. The reactivity of 1PF₆ was investigated. On one hand, the reaction of 1PF₆ with N-chlorosuccinimide or N-bromosuccinimide provides the haloderivatives [IrX{κ³C,P,P′-(SiNP–H)}(CN^tBu)₂][PF₆] (X = Cl, 4PF₆; Br, 5PF₆), and the reaction of 5PF₆ with AgPF₆ in the presence of acetonitrile affords the solvato species [Ir{κ³C,P,P′-(SiNP–H)}(CH₃CN)(CN^tBu)₂]²⁺ (6²⁺) isolated as the hexafluorophosphate salt. On the other hand, the reaction of 1PF₆ with HBF₄ gives the iridium(III) compound [IrH(CH₂SiF₂CH₃)(HNP)₂(CN^tBu)₂][BF₄] (7BF₄) as the result of the formal addition of hydrogen fluoride to the Si–N bonds of 1⁺ [HNP = HN(4-tolyl)PPh₂]. A similar outcome was observed in the reaction of 1PF₆ with CF₃COOH rendering 7PO₂F₂. In this case the intermediate [IrH{κ²C,P-CH₂SiMeFN(4-tolyl)PPh₂}(HNP)(CN^tBu)₂]⁺ (8⁺) was observed and characterised in situ by NMR spectroscopy. DFT calculations suggests that the reaction goes through the sequential protonation of the nitrogen atom of the Si–N–P moiety followed by the formal addition of fluoride ion to silicon. Also, the crystal structures of SiNP, 1PF₆, 4PF₆ and 7BF₄ have been determined by X-ray diffraction measurements.