Alkoxylation and Amination of Ring-Methyl Group in Pentamethylcyclopentadienyliridium Complexes
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- 作者：Ken-ichi Fujita ; Masashi Nakamura ; and Ryohei Yamaguchi
- 刊名：Organometallics
- 出版年：2001
- 出版时间：January 8, 2001
- 年：2001
- 卷：20
- 期：1
- 页码：100 - 105
- 全文大小：83K
- 年卷期：v.20,no.1(January 8, 2001)
- ISSN：1520-6041
文摘
Reactions of a unidentate bis(diphenylphosphino)methane (dppm) complex Cp*IrCl2(
1-dppm) (1) with 2 equiv of NaOR (R = Et, Me, or iPr) give ring-methyl-alkoxylated complexes(C5Me4CH2OR)Ir(2-dppm) [R = Et (5a); R = Me (5b); R = iPr (5c)], respectively. Cationiccomplexes [Cp*IrCl(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 [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-rayanalysis.
1-dppm) (1) with 2 equiv of NaOR (R = Et, Me, or iPr) give ring-methyl-alkoxylated complexes(C5Me4CH2OR)Ir(2-dppm) [R = Et (5a); R = Me (5b); R = iPr (5c)], respectively. Cationiccomplexes [Cp*IrCl(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 [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-rayanalysis.