Intramolecular C–H Oxidative Addition to Iridium(I) in Complexes Containing a N,N′‑Diphosphanosilanediamine Ligand
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https://figshare.com/articles/dataset/Intramolecular_C_H_Oxidative_Addition_to_Iridium_I_in_Complexes_Containing_a_i_N_i_i_N_i_Diphosphanosilanediamine_Ligand/2330707
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The iridium(I) complexes of formula Ir(cod)(SiNP)+ (1+) and IrCl(cod)(SiNP) (2) are easily obtained from the reaction of SiMe2{N(4-C6H4CH3)PPh2}2 (SiNP) with [Ir(cod)(CH3CN)2]+ or [IrCl(cod)]2, respectively. The carbonylation of [1][PF6] affords the cationic pentacoordinated complex [Ir(CO)(cod)(SiNP)]+ (3+), while the treatment 2 with CO gives the cation 3+ as an intermediate, finally affording an equilibrium mixture of IrCl(CO)(SiNP) (4) and the hydride derivative of formula IrHCl(CO)(SiNP–H) (5) resulting from the intramolecular oxidative addition of the C–H bond of the SiCH3 moiety to the iridium(I) center. Furthermore, the prolonged exposure of [3]Cl or 2 to CO resulted in the formation of the iridium(I) pentacoordinated complex Ir(SiNP–H)(CO)2 (6). The unprecedented κ3C,P,P′ coordination mode of the [SiNP–H] ligand observed in 5 and 6 has been fully characterized in solution by NMR spectroscopy. In addition, the single-crystal X-ray structure of 6 is reported.
创建时间：
2016-02-18
