Abstract
Reactions of a unidentate bis(diphenylphosphino)methane (dppm) complex Cp*IrCl2(η1-dppm) (1) with 2 equiv of NaOR (R = Et, Me, or iPr) give ring-methyl-alkoxylated complexes (C5Me4CH2OR)Ir(η2-dppm) [R = Et (5a); R = Me (5b); R = iPr (5c)], respectively. Cationic complexes [Cp*IrCl(η2-dppm)]OTf (2), [Cp*IrCl{P(OPh)3}2]OTf (3), and [Cp*IrCl(PPh3)2]OTf (4) react with 2 equiv of NaOEt to give (C5Me4CH2OEt)IrL2 [L2 = dppm (5a); L = P(OPh)3 (6a); L = PPh3 (7a)], respectively. The complex 3 reacts with 2 equiv of NaOtBu in ethanol, methanol, 2-propanol, allyl alcohol, or propargyl alcohol to give (C5Me4CH2OR)Ir{P(OPh)3}2 [R = Et (6a); R = Me (6b); R = iPr (6c); R = allyl (6d); R = propargyl (6e)], respectively. Furthermore, treatment of 3 with 2 equiv of nBuLi and excess diethylamine, propylamine, N-methylaniline, or aniline in triethylamine as solvent gives ring-methyl aminated complexes (C5Me4CH2NR1R2)Ir{P(OPh)3}2 [R1 = R2 = Et (8a); R1 = nPr, R2 = H (8b); R1 = Ph, R2 = Me (8c); R1 = Ph, R2 = H (8d)], respectively. The structure of 8a has been confirmed by X-ray analysis.
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