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

The iridium(III) hydride compound [IrH{κ³C,P,P'-(SiNP-H)}(CNBu)₂][PF₆] (1PF₆) was obtained by reaction of [Ir(SiNP)(cod)][PF₆] with CNBu 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)(CNBu)][PF₆] (2PF₆) forms in the first place and that further reacts with CNBu, affording the square planar intermediate [Ir(SiNP)(CNBu)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)}(CNBu)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)(CNBu)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(CNBu)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)(CNBu)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.