Direct observation of a 14-electron ruthenacyclobutane relevant to olefin metathesis

被引:155
作者
Romero, PE [1 ]
Piers, WE [1 ]
机构
[1] Univ Calgary, Calgary, AB T2N 1N4, Canada
关键词
D O I
10.1021/ja042259d
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The 14-electron ruthenium phosphonium alkylidene complex [(IH2Mes)Cl2Ru=CH(PCy3)][B(C6F5)4], 1b, a highly active olefin metathesis catalyst, reacts with stoichiometric quantities of ethylene at -50 °C in CD2Cl2 to generate the ruthenacyclobutane complex [(IH2Mes)Cl2RuCH2CH2CH2], 2, and [CH2=CH(PCy3)][B(C6F5)4] in quantitative yield by NMR spectroscopy. 1H and 13C NMR spectroscopies on 2 and 2-13C3 are consistent with a symmetrical C2v structure, providing the first experimental information concerning this crucial intermediate in ruthenium-mediated olefin metathesis. At -50 °C, exchange with free ethylene takes place on the chemical time scale. Complex 2 decomposes in solution upon warming to room temperature, generating propene and unknown ruthenium product(s). Copyright © 2005 American Chemical Society.
引用
收藏
页码:5032 / 5033
页数:2
相关论文
共 27 条
[11]  
Grubbs R.H., 2003, HDB METATHESIS, V3
[12]   H-1, C-13 AND PT-195 NMR-STUDIES OF SOME PLATINUM-CYCLOPROPANE COMPOUNDS [J].
HALL, PW ;
PUDDEPHATT, RJ ;
TIPPER, CFH .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1974, 71 (01) :145-151
[13]   TITANIUM METALLACARBENE-METALLACYCLOBUTANE REACTIONS - STEPWISE METATHESIS [J].
HOWARD, TR ;
LEE, JB ;
GRUBBS, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (22) :6876-6878
[14]   METALLACYCLOBUTANE COMPLEXES OF THE GROUP-8 TRANSITION-METALS - SYNTHESIS, CHARACTERIZATIONS, AND CHEMISTRY [J].
JENNINGS, PW ;
JOHNSON, LL .
CHEMICAL REVIEWS, 1994, 94 (08) :2241-2290
[15]   A recyclable Ru-based metathesis catalyst [J].
Kingsbury, JS ;
Harrity, JPA ;
Bonitatebus, PJ ;
Hoveyda, AH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (04) :791-799
[16]   KINETICS AND STEREOCHEMISTRY OF THE TITANACYCLOBUTANE TITANAMETHYLENE INTERCONVERSION - INVESTIGATION OF A DEGENERATE OLEFIN METATHESIS REACTION [J].
LEE, JB ;
OTT, KC ;
GRUBBS, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (26) :7491-7496
[17]   C-C and C-H bond activation at ruthenium(II): The stepwise degradation of a neopentyl ligand to a trimethylenemethane ligand [J].
McNeill, K ;
Andersen, RA ;
Bergman, RG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (46) :11244-11254
[18]   Rapidly initiating ruthenium olefin-metathesis catalysts [J].
Romero, PE ;
Piers, WE ;
McDonald, R .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (45) :6161-6165
[19]  
Sanford MS, 2000, ANGEW CHEM INT EDIT, V39, P3451, DOI 10.1002/1521-3773(20001002)39:19<3451::AID-ANIE3451>3.0.CO
[20]  
2-U