Alkoxylation and amination of ring-methyl group in pentamethylcyclopentadienyliridium complexes

Reactions of a unidentate bis(diphenylphosphino)methane (dppm) complex Cp*IrCl2(eta (1)-dppm) (1) with 2 equiv of NaOR (R = Et, Me, or Pr-i) give ring-methyl-alkoxylated complexes (C5Me4CH2OR)Ir(eta (2)-dppm) [R = Et (5a); R = Me (5b); R = Pr-i (5c)], respectively. Cationic complexes [Cp*IrCl(eta (2)-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 [L-2 = dppm (5a); L = P(OPh)(3) (6a); L = PPh3 (7a)], respectively. The complex 3 reacts with 2 equiv of (NaOBu)-Bu-t 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 = Pr-i (6c) R = allyl (6d); R = propargyl (6e)], respectively. Furthermore, treatment of 3 with 2 equiv of (BuLi)-Bu-n and excess diethylamine, propylamine, N-methylaniline, or aniline in triethylamine as solvent gives ring-methyl aminated complexes ((C5Me4CH2NRR2)-R-1)Ir(P(OPh)(3))(2) [R-1 = R-2 = Et (8a); R-1 = Pr-n, R-2 = H (sb); R-1 = Ph, R-2 = Me (8c); R-1 = Ph, R-2, H (8d)], respectively. The structure of 8a has been confirmed by X-ray analysis.