Alkoxylation and amination of ring-methyl group in pentamethylcyclopentadienyliridium complexes

被引:13
作者
Fujita, K [1 ]
Nakamura, M
Yamaguchi, R
机构
[1] Kyoto Univ, Fac Integrated Human Studies, Dept Nat Environm Sci, Kyoto 6068501, Japan
[2] Kyoto Univ, Grad Sch Human & Environm Studies, Kyoto 6068501, Japan
关键词
D O I
10.1021/om000718n
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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.
引用
收藏
页码:100 / 105
页数:6
相关论文
共 29 条
  • [1] Abel E. W., 1995, COMPREHENSIVE ORGANO
  • [2] CHIRAL CYCLOPENTADIENYL CATALYSTS .3. SYNTHESIS AND REACTIONS OF (S)-1-(1-DIMETHYLAMINOETHYL)-2-(2,3,4,5-TETRAMETHYLCYCLOPENTA-1,3-DIENYL)BENZENE - CRYSTAL-STRUCTURE OF [RH(ETA-5-C5ME4C6H4CH(ME)NME2)CL2]
    ADAMS, H
    BAILEY, NA
    COLLEY, M
    SCHOFIELD, PA
    WHITE, C
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1994, (09): : 1445 - 1451
  • [3] SYNTHESIS AND STRUCTURE OF [(ETA-C5ME5)IR(CO)]2
    BALL, RG
    GRAHAM, WAG
    HEINEKEY, DM
    HOYANO, JK
    MCMASTER, AD
    MATTSON, BM
    MICHEL, ST
    [J]. INORGANIC CHEMISTRY, 1990, 29 (10) : 2023 - 2025
  • [4] BEURSKENS PT, 1992, PATTY
  • [5] BEURSKENS PT, 1994, DIRDIF94
  • [6] MONOSUBSTITUTED CYCLOPENTADIENYL HALF-SANDWICH TRANSITION-METAL COMPLEXES
    COVILLE, NJ
    DUPLOOY, KE
    PICKL, W
    [J]. COORDINATION CHEMISTRY REVIEWS, 1992, 116 : 1 - 267
  • [7] CREAGH DC, 1992, INT TABLES XRAY CRYS, VC
  • [8] EXCITED-STATES OF MIXED-LIGAND CHELATES OF RUTHENIUM(II) AND RHODIUM(III)
    CROSBY, GA
    ELFRING, WH
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1976, 80 (20) : 2206 - 2211
  • [9] RING-METHYL ACTIVATION IN PENTAMETHYLCYCLOPENTADIENYL COMPLEXES .4. SYNTHESES, STRUCTURES, AND REACTIONS OF [(C(5)ME(4)CH(2)CL)RUCL(CO)(2)] AND RELATED-COMPOUNDS - X-RAY STRUCTURES OF [(C(5)ME(4)CH(2)CL)RUCL(CO)(2)] AND[(C(5)ME(4)CH(2)OET)RU(PPH(3))(CO)(2)](OTF)
    FAN, L
    TURNER, ML
    ADAMS, H
    BAILEY, NA
    MAITLIS, PM
    [J]. ORGANOMETALLICS, 1995, 14 (02) : 676 - 684
  • [10] Ring-methyl activation in pentamethylcyclopentadienyl complexes .5. Syntheses and structures of tetramethylfulvene complexes of ruthenium(II)
    Fan, L
    Wei, CH
    Aigbirhio, FI
    Turner, ML
    Gusev, OV
    Morozova, LN
    Knowles, DRT
    Maitlis, PM
    [J]. ORGANOMETALLICS, 1996, 15 (01) : 98 - 104