An electron-deficient Iridium(III) dihydride complex capable of intramolecular C-H activation

被引：89
作者：
Scott, NM
Pons, V
Stevens, ED
Heinekey, DM
Nolan, SP [1 ]
机构：
[1] Univ New Orleans, Dept Chem, New Orleans, LA 70148 USA
[2] Univ Washington, Dept Chem, Seattle, WA 98195 USA
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2005年 / 44卷 / 17期
关键词：
agostic interactions; C-H activation; carbene ligands; coordination modes; iridium;
D O I：
10.1002/anie.200463000
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
(Chemical Equation Presented) Double take: A remarkable electron-deficient cationic dihydride complex [Ir-(ItBu)2(H)2](PF 6) (see crystal structure), prepared in high yield from the reaction of 14-electron complex [Ir(ItBu′)2](PF6) and H 2 gas, shows a rare agostic interaction. The reaction illustrates the reversibility of a double, intramolecular C-H activation process and provides a rare example of a "proposed" intermediate. ItBu: N,N′-di(tert- butyl)imidazol-2-ylidene. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.
引用
收藏
页码：2512 / 2515
页数：4
相关论文
共 27 条
[11]   tert-butyl is superior to phenyl as an agostic donor to 14-electron Ir(III) [J].
Cooper, AC ;
Streib, WE ;
Eisenstein, O ;
Caulton, KG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (38) :9069-9070
[12]   16-electron, non-π-stabilized Ir(H)2(H2)(PBu2tPh)2+ and 18-electron Ir(H)2(H2)2(PBu2tPh)2+:: fluxionality and H/D exchange as independent processes [J].
Cooper, AC ;
Eisenstein, O ;
Caulton, KG .
NEW JOURNAL OF CHEMISTRY, 1998, 22 (04) :307-309
[13]   DIHYDROGEN COMPLEXES - SOME STRUCTURAL AND CHEMICAL STUDIES [J].
CRABTREE, RH .
ACCOUNTS OF CHEMICAL RESEARCH, 1990, 23 (04) :95-101
[14]   Double C-H activation in a Rh-NHC complex leading to the isolation of a 14-electron Rh(III) complex [J].
Dorta, R ;
Stevens, ED ;
Nolan, SP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (16) :5054-5055
[15]   Reactivity of [Ir(COE)2(solvent)2]PF6 complexes toward alkylphosphines:: Room-temperature C-H activation (cyclometalation) and isolation of a 14-electron alkyl-iridium(III) complex [J].
Dorta, R ;
Goikhman, R ;
Milstein, D .
ORGANOMETALLICS, 2003, 22 (13) :2806-2809
[16]  
HERMANN WA, 1997, ANGEW CHEM, V109, P1074
[17]   Organometallic homogeneous catalysis - Quo vadis? [J].
Herrmann, WA ;
Cornils, B .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1997, 36 (10) :1048-1067
[18]   The first eta(2)-CH2Cl2 adduct of Ru(II):[RuH(eta(2)-CH2Cl2)(CO)((PBu2Me)-Bu-t)(2)][BAr4'] (Ar' equals 3,5-C6H3(CF3)(2)) and its RuH(CO)((PBu2Me)-Bu-t)(2)(+) precursor [J].
Huang, DJ ;
Huffman, JC ;
Bollinger, JC ;
Eisenstein, O ;
Caulton, KG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (31) :7398-7399
[19]  
Kubas G.J., 2001, METAL DIHYDROGEN SIG
[20]   A cationic iridium complex bearing an imidazol-2-ylidene ligand as alkene hydrogenation catalyst [J].
Lee, HM ;
Jiang, T ;
Stevens, ED ;
Nolan, SP .
ORGANOMETALLICS, 2001, 20 (06) :1255-1258
123