Direct preparation of [Ru(η2-O2CO)(η6-arene)(L)] carbonate complexes (L = phosphane, carbene) and their use as precursors of [RuH2(p-cymene)(PCy3)] and [Ru(η6-arene)(L)(MeCN)2][BF4]2:: X-ray crystal structure determination of [Ru(η2-O2CO)(p-cymene)(PCy3)]•1/2CH2Cl2 and [Ru(η2-O2CO)(η6-C6Me6)-(PMe3)]•H2O

被引:43
作者
Demerseman, B [1 ]
Mbaye, MD [1 ]
Sémeril, D [1 ]
Toupet, L [1 ]
Bruneau, C [1 ]
Dixneuf, PH [1 ]
机构
[1] Univ Rennes 1, CNRS, UMR 6509, Inst Chim Rennes, F-35042 Rennes, France
关键词
arene ligands; hydrides; O ligands; reactive intermediates; ruthenium;
D O I
10.1002/ejic.200500973
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
[RuCL2(eta(6)-arene)(PR3)] complexes react with K2CO3 in the presence of water to afford the carbonatoruthenium(ii) derivatives [Ru(eta(2)-O2CO)(eta(6)-arene)(PR3)] (2; arene = p-cymene, R = Cy, Ph, or Me; arene = hexamethylbenzene, R = Me) involving a planar Ru(eta(2)-O2CO) moiety as shown by X-ray crystal structure determination of 2a (p-cymene, PCy3) and 2d (hexamethylbenzene, PMe3). The complex [Ru(eta(2)-O2CO)(p-cymene)(PCy3)] is cleanly converted in hot methanol into the dihydride [RuH2(p-cymene)(PCy3)]. The related complexes [Ru(eta(2)-O2CO)(eta(6)-arene)(IMes)] [arene = p-cymene or hexamethylbenzene, IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] are straightforwardly prepared by treating [RuCl2(eta(6)-arene)](2) precursors with 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride and K2CO3 in THF at reflux. The removal of the carbonato ligand from complexes 2 with HBF4 in the presence of acetonitrile leads to the dicationic derivatives [Ru(eta(6)-arene)(L)(MeCN)(2)][BF4](2) (L = PR3 or IMes). ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
引用
收藏
页码:1174 / 1181
页数:8
相关论文
共 49 条
[1]   SIR97:: a new tool for crystal structure determination and refinement [J].
Altomare, A ;
Burla, MC ;
Camalli, M ;
Cascarano, GL ;
Giacovazzo, C ;
Guagliardi, A ;
Moliterni, AGG ;
Polidori, G ;
Spagna, R .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1999, 32 :115-119
[2]   A STABLE CARBENE ALANE ADDUCT [J].
ARDUENGO, AJ ;
DIAS, HVR ;
CALABRESE, JC ;
DAVIDSON, F .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (24) :9724-9725
[3]   Looking for stable carbenes: The difficulty in starting anew [J].
Arduengo, AJ .
ACCOUNTS OF CHEMICAL RESEARCH, 1999, 32 (11) :913-921
[4]  
ARDUENGO AJ, 1993, Patent No. 5182405
[5]   OLIGOPHOSPHINE LIGANDS .38. PREPARATION, ISOMERISM, AND REACTIVITY OF ARYLHYDRIDORUTHENIUM(II) COMPLEXES [MESI(CH2PME2)3]ME3P)RUH(AR) [J].
BECKER, C ;
DAHLENBURG, L ;
KERSTAN, S .
ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES, 1993, 48 (05) :577-582
[6]   The development of palladium catalysts for C-C and C-heteroatom bond forming reactions of aryl chloride substrates [J].
Bedford, RB ;
Cazin, CSJ ;
Holder, D .
COORDINATION CHEMISTRY REVIEWS, 2004, 248 (21-24) :2283-2321
[7]   Synthesis and reactivity of η6-arene ruthenium anilide complexes [J].
Boncella, JM ;
Eve, TM ;
Rickman, B ;
Abboud, KA .
POLYHEDRON, 1998, 17 (5-6) :725-736
[8]   η6-mesityl,η1-imidazolinylidene-carbene-ruthenium(II) complexes:: Catalytic activity of their allenylidene derivatives in alkene metathesis and cycloisomerisation reactions [J].
Çetinkaya, B ;
Demir, S ;
Özdemir, I ;
Toupet, L ;
Sémeril, D ;
Bruneau, C ;
Dixneuf, PH .
CHEMISTRY-A EUROPEAN JOURNAL, 2003, 9 (10) :2323-2330
[9]   ISOCYANIDE COMPLEXES OF ZEROVALENT RUTHENIUM - PROTON ADDITION TO A TRANSITION-METAL BASE OFFERING ALTERNATIVE BASE SITES [J].
CHRISTIAN, DF ;
ROPER, WR .
JOURNAL OF THE CHEMICAL SOCIETY D-CHEMICAL COMMUNICATIONS, 1971, (20) :1271-+
[10]   FURTHER STUDY OF TETRACARBONATO DIRUTHENIUM(II,III) COMPOUNDS [J].
COTTON, FA ;
LABELLA, L ;
SHANG, M .
INORGANIC CHEMISTRY, 1992, 31 (12) :2385-2389