Modular assembly of a chiral bis(oxazolinyl)carbene:: A new meridionally coordinating tridentate spectator ligand

被引:32
作者
Schneider, N
César, V
Bellemin-Laponnaz, S
Gade, LH
机构
[1] Heidelberg Univ, Inst Anorgan Chem, D-69120 Heidelberg, Germany
[2] Univ Strasbourg, Inst Le Bel, Lab Chim Organomet & Catalyse, F-67000 Strasbourg, France
关键词
D O I
10.1021/om0506769
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A highly modular assembly of meridionally coordinating tridentate bis(oxazoline)carbene ligands ('BoxCarb') is reported, in which the coupling of the oxazoline units with the central imidazolidene ring occurs by means of chemically orthogonal reaction steps. Reaction of the imidazolium salt (iPr)(2)-BoxCarbH(+)Br(-) 4 with [Rh(OtBu)(nbd)](2) at temperatures below -30 degrees C gave a thermally unstable rhodium(I) species, which was directly reacted at -78 degrees C with 1 molar equiv of bromine, giving the rhodium(III) compound [RhBr3((iPr)(2)-BoxCarb)] (5). An X-ray diffraction study established the meridional tricoordination of the ligand. Reacting 4 with 0.5 molar equiv of Ag2O gave the silver(I) complex 6, which was converted with [PdCl2(COD)] in CH2Cl2 to give the cationic square planar palladium(II) complex [PdCl((iPr)(2)-BoxCarb)]Cl (7).
引用
收藏
页码:4886 / 4888
页数:3
相关论文
共 32 条
[1]   Looking for stable carbenes: The difficulty in starting anew [J].
Arduengo, AJ .
ACCOUNTS OF CHEMICAL RESEARCH, 1999, 32 (11) :913-921
[2]   Chelating alkoxy-N-heterocyclic carbene complexes of silver and copper [J].
Arnold, PL ;
Scarisbrick, AC ;
Blake, AJ ;
Wilson, C .
CHEMICAL COMMUNICATIONS, 2001, (22) :2340-2341
[3]   Synthesis of new chiral N-heterocyclic carbene-imine ligands and their application to an asymmetric allylic alkylation reaction [J].
Bonnet, LG ;
Douthwaite, RE ;
Kariuki, BM .
ORGANOMETALLICS, 2003, 22 (21) :4187-4189
[4]   Stable carbenes [J].
Bourissou, D ;
Guerret, O ;
Gabbaï, FP ;
Bertrand, G .
CHEMICAL REVIEWS, 2000, 100 (01) :39-91
[5]   Direct coupling of oxazolines and N-heterocyclic carbenes:: A modular approach to a new class of C-N donor ligands for homogeneous catalysis [J].
César, V ;
Bellemin-Laponnaz, S ;
Gade, LH .
ORGANOMETALLICS, 2002, 21 (24) :5204-5208
[6]   Designing the "search pathway" in the development of a new class of highly efficient stereoselective hydrosilylation catalysts [J].
César, V ;
Bellemin-Laponnaz, S ;
Wadepohl, H ;
Gade, LH .
CHEMISTRY-A EUROPEAN JOURNAL, 2005, 11 (09) :2862-2873
[7]   Chiral N-heterocyclic carbenes as stereodirecting ligands in asymmetric catalysis [J].
César, V ;
Bellemin-Laponnaz, S ;
Gade, LH .
CHEMICAL SOCIETY REVIEWS, 2004, 33 (09) :619-636
[8]   Cationic and neutral rhodium(I) oxazolinylcairbene complexes [J].
César, V ;
Bellemin-Laponnaz, S ;
Gade, LH .
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2004, (17) :3436-3444
[9]   Synthesis and structural characterisation of stable pyridine- and phosphine-functionalised N-heterocyclic carbenes [J].
Danopoulos, AA ;
Winston, S ;
Gelbrich, T ;
Hursthouse, MB ;
Tooze, RP .
CHEMICAL COMMUNICATIONS, 2002, (05) :482-483
[10]   Pyridine-2,6-bis(oxazolines), helpful ligands for asymmetric catalysts [J].
Desimoni, G ;
Faita, G ;
Quadrelli, P .
CHEMICAL REVIEWS, 2003, 103 (08) :3119-3154