Synthesis and reactivity of η6-arene ruthenium anilide complexes

被引:31
作者
Boncella, JM [1 ]
Eve, TM
Rickman, B
Abboud, KA
机构
[1] Univ Florida, Dept Chem, Gainesville, FL 32611 USA
[2] Univ Florida, Ctr Catalysis, Gainesville, FL 32611 USA
关键词
eta(6)-arene ruthenium anilide complexes; unsaturated electrophilic reagents; CO2; DMAD;
D O I
10.1016/S0277-5387(97)00373-2
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The compounds, (eta(6)-C6Me6)Ru(PMe3)(R)(NR'R"); (R=Ph, R'=H, R"=Ph, 3; R=Me, R'=H, R"=Ph, 4; R=Ph, R'=H; R"=p-tol, 5; R=Me, R'=Me, R"=Ph, 6) are synthesized through the interaction of (eta(6)-C6Me6)Ru(PMe3)(R)(I) and the corresponding anilide salt, KNR'R" in THF at low temperature. The reactions between these complexes and the unsaturated electrophilic reagents, CO2 and dimethylacetylene dicarboxylate (DMAD) have been described. The typical reaction involves net insertion of the electrophile into the Ru anilide bond. Complex 6 reacts with H2O giving the hydroxide complex, 11, which reacts with CO2 giving the bicarbonato complex, 12. The X-ray crystal structure of 3 is reported. Compound 3 crystallizes in the monoclinic space group, P2(1)/n, a = 12.013(2) Angstrom, b = 16.700(3) Angstrom, c = 12.414(1) Angstrom, beta = 97.35(2), V = 2470.0(7) Angstrom(3) and Z = 4. (C) 1998 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:725 / 736
页数:12
相关论文
共 35 条
[11]   IRIDIUM ALKOXIDE AND AMIDE HYDRIDE COMPLEXES - SYNTHESIS, REACTIVITY, AND THE MECHANISM OF O-H AND N-H REDUCTIVE ELIMINATION [J].
GLUECK, DS ;
WINSLOW, LJN ;
BERGMAN, RG .
ORGANOMETALLICS, 1991, 10 (05) :1462-1479
[12]   SYNTHESIS, CHARACTERIZATION, AND REACTIVITY OF ALKOXIDE AND HYDROXIDE COMPLEXES OF RHODIUM(I) AND IRIDIUM(I) [J].
GREEN, LM ;
MEEK, DW .
ORGANOMETALLICS, 1989, 8 (03) :659-666
[13]   SYNTHESIS OF A HIGHLY REACTIVE (BENZYNE)RUTHENIUM COMPLEX - C-C, C-H, N-H, AND O-H ACTIVATION REACTIONS [J].
HARTWIG, JF ;
ANDERSEN, RA ;
BERGMAN, RG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (07) :2717-2719
[14]   SYNTHESIS AND CHEMISTRY OF RUTHENIUM HYDRIDO ARYLOXIDES AND ARYLAMIDES - AN INVESTIGATION OF STRUCTURE, N-H AND O-H ELIMINATION PROCESSES, PROTON-CATALYZED EXCHANGE-REACTIONS, AND RELATIVE RU-X BOND STRENGTHS [J].
HARTWIG, JF ;
ANDERSEN, RA ;
BERGMAN, RG .
ORGANOMETALLICS, 1991, 10 (06) :1875-1887
[15]   PREPARATION AND CONFORMATIONAL DYNAMICS OF (C5ME5)RH(PR'3)RX - HINDERED ROTATION ABOUT RHODIUM-PHOSPHORUS AND RHODIUM-CARBON BONDS [J].
JONES, WD ;
FEHER, FJ .
INORGANIC CHEMISTRY, 1984, 23 (16) :2376-2388
[16]   INSERTION OF (ETA-5-C5ME5)(PME3)IR INTO THE C-H BONDS OF FUNCTIONALIZED ORGANIC-MOLECULES - A C-H ACTIVATION ROUTE TO 2-OXAMETALLACYCLOBUTANES AND 2-AZAMETALLACYCLOBUTANES, POTENTIAL MODELS FOR OLEFIN OXIDATION INTERMEDIATES [J].
KLEIN, DP ;
HAYES, JC ;
BERGMAN, RG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (11) :3704-3706
[17]   EVIDENCE FOR AN UNPRECEDENTED IR(H)(NH3) REVERSIBLE IR(H2)(NH2) EQUILIBRIUM AND HYDROGEN-EXCHANGE BETWEEN NH AND CH BONDS [J].
KOELLIKER, R ;
MILSTEIN, D .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (22) :8524-8525
[18]  
LAPPERT MF, 1980, METAL METALLOID AMID, P488
[19]   PREPARATION, SOLUTION DYNAMICS, AND X-RAY CRYSTAL-STRUCTURE OF THE ANILIDE-BRIDGED DIRUTHENIUM COMPLEX [(ETA-6-C6ME6)2RU2(MU-NHPH)3][BF4] [J].
MARTIN, GC ;
PALENIK, GJ ;
BONCELLA, JM .
INORGANIC CHEMISTRY, 1990, 29 (10) :2027-2030
[20]   SYNTHESIS OF RUTHENIUM AMIDE COMPLEXES BY NUCLEOPHILIC-ATTACK ON ORTHO-METALATED IMINE LIGANDS [J].
MARTIN, GC ;
BONCELLA, JM ;
WUCHERER, EJ .
ORGANOMETALLICS, 1991, 10 (08) :2804-2811