ACID-CATALYZED ISOMERIZATION AND DEUTERIUM-EXCHANGE OF RHENIUM ALKENE COMPLEXES VIA IN-PLACE ROTATION OF AN AGOSTIC ALKYLRHENIUM CATION

被引：22

作者：

CASEY, CP

YI, CS

机构：

[1] Department of Chemistry, University of Wisconsin-Madison, Madison

来源：

ORGANOMETALLICS | 1991年 / 10卷 / 01期

关键词：

D O I：

10.1021/om00047a018

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

C5H5(CO)2Re(cis-CH3CH = CHCH3) (1) isomerized to a 45:55 equilibrium mixture of 1 and C5H5-(CO)2Re(trans-CH3CH = CHCH3) (2) upon treatment with CF3CO2H in CH2Cl2. In the isomerization of 1 by CF3CO2D, the initially formed 2 was monodeuterated at the vinyl position. Treatment of C5H5(CO)2Re(CH2 = CHCH2CH3) (3) with CF3CO2D led only to deuterium exchange of the vinyl hydrogens; no formation of 1 or 2 was observed. These data are consistent with a mechanism involving agostic rhenium alkyl complexes that undergo "in-place rotation" and deprotonation much more rapidly than formation of a free alkylrhenium intermediate.

引用

收藏

页码：33 / 35

页数：3

相关论文

共 14 条

[1] A NEW MECHANISM FOR EXCHANGE PROCESSES OBSERVED IN THE COMPOUNDS [NB(ETA-C5H5)2(EXO-ETA-RCH=CH2)H], [TA(ETA-C5H5)2(EXO-ETA-RCH=CH2)H] [J].

BERCAW, JE ;

BURGER, BJ ;

GREEN, MLH ;

SANTARSIERO, BD ;

SELLA, A ;

TRIMMER, MS ;

WONG, LL .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (11) :734-736

[2] LIGAND AND SUBSTITUENT EFFECTS ON THE DYNAMICS AND STRUCTURE OF AGOSTIC COMPLEXES OF THE TYPE C5R5(L)CO(CH2CHR'-MU-H)+BF4-(L = P(OME)3, PME3, R = H, ME, R' = H, ME) [J].

BROOKHART, M ;

LINCOLN, DM ;

VOLPE, AF ;

SCHMIDT, GF .

ORGANOMETALLICS, 1989, 8 (05) :1212-1218

[3]

BROOKHART M, 1988, PROG INORG CHEM, V36, P1

[4] CARBON-HYDROGEN-TRANSITION METAL BONDS [J].

BROOKHART, M ;

GREEN, MLH .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1983, 250 (01) :395-408

[5] AMPHIPHILIC CARBENE COMPLEXES - BOTH ELECTROPHILES AND NUCLEOPHILES ATTACK THE CARBENE CARBON OF C5H5(CO)2RE=CHR [J].

CASEY, CP ;

VOSEJPKA, PC ;

ASKHAM, FR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (09) :3713-3715

[6] SYNTHESIS OF CATIONIC (PI-ALLYL)RHENIUM COMPLEXES AND THEIR REACTIONS WITH CARBON NUCLEOPHILES [J].

CASEY, CP ;

YI, CS .

ORGANOMETALLICS, 1990, 9 (09) :2413-2414

[7] SYNTHESIS OF RHENIUM ALKENE COMPLEXES FROM THE REACTION OF THE HETEROBIMETALLIC DIHYDRIDE C5H5(CO)2HRE-PTH(PPH3)2 WITH ALKYNES [J].

CASEY, CP ;

RUTTER, EW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (24) :8917-8919

[8]

CASEY CP, UNPUB

[9] COORDINATION CHEMISTRY OF THE MANGANESE AND RHENIUM FRAGMENTS (C5H5)M(CO)2 [J].

CAULTON, KG .

COORDINATION CHEMISTRY REVIEWS, 1981, 38 (01) :1-43

[10] KINETICS AND MECHANISM OF THE INSERTION OF OLEFINS INTO TRANSITION-METAL HYDRIDE BONDS [J].

DOHERTY, NM ;

BERCAW, JE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (09) :2670-2682