DOUBLE-INSERTION REACTION OF ALKYNES WITH [CP'2ZRME]+ - FORMATION OF AN UNUSUAL DISTORTED ETA-5-PENTADIENYL LIGAND

被引：80

作者：

HORTON, AD ^{[1
]}

ORPEN, AG ^{[1
]}

机构：

[1] UNIV BRISTOL,SCH CHEM,BRISTOL BS8 1TS,AVON,ENGLAND

来源：

ORGANOMETALLICS | 1992年 / 11卷 / 01期

关键词：

D O I：

10.1021/om00037a005

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of [Cp'2ZrMe(NMe2Ph)][X] (1; Cp' = C5H5 (a), (Me3Si)C5H4 (b), (Me3C)C5H4 (c), rac-C2H4(indenyl)2 (d); [X]- = [B(4-C6H4F)4]-) with excess 2-butyne gives [Cp'2Zr(eta(5)-CH2C(Me) = C(Me)C(Me) = CHMe)][X] (2a-d); an X-ray structure analysis of 2c shows that novel pentadienyl coordination occurs via a sigma-bond and two weak unconjugated eta(2)-interactions with the double bonds. The reaction proceeds via observable, but unstable, alkenyl and 1,3-alkadienyl complexes, followed by a 1,5-hydrogen shift. Double alkyne insertion is unfavorable for crowed (C5Me5)2ZrMe(X), which instead gives [C5Me5)2Zr(eta(3)-CH2C = CMe)][X] via a sigma-bond metathesis reaction.

引用

收藏

页码：8 / 10

页数：3

相关论文

共 32 条

[1] ETA-4-SYN-TRANS-1,3-DIENES AS LIGANDS FOR CATIONIC MOLYBDENUM CENTERS [J].

BENYUNES, SA ;

GREEN, M ;

GRIMSHIRE, MJ .

ORGANOMETALLICS, 1989, 8 (09) :2268-2270

[2] BASE-FREE CATIONIC 14-ELECTRON TITANIUM AND ZIRCONIUM ALKYLS - INSITU GENERATION, SOLUTION STRUCTURES, AND OLEFIN POLYMERIZATION ACTIVITY [J].

BOCHMANN, M ;

JAGGAR, AJ ;

NICHOLLS, JC .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1990, 29 (07) :780-782

[3] ETHYLENE INSERTION AND BETA-HYDROGEN ELIMINATION FOR PERMETHYLSCANDOCENE ALKYL COMPLEXES - A STUDY OF THE CHAIN PROPAGATION AND TERMINATION STEPS IN ZIEGLER-NATTA POLYMERIZATION OF ETHYLENE [J].

BURGER, BJ ;

THOMPSON, ME ;

COTTER, WD ;

BERCAW, JE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (04) :1566-1577

[4] INSERTION AND SIGMA-BOND METATHESIS PATHWAYS IN GAS-PHASE REACTIONS OF BIS(ETA-5-CYCLOPENTADIENYL)METHYLZIRCONIUM(1+) WITH DIHYDROGEN AND UNSATURATED-HYDROCARBONS [J].

CHRIST, CS ;

EYLER, JR ;

RICHARDSON, DE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (02) :596-607

[5]

CLARKE TC, 1989, J AM CHEM SOC, V105, P7787

[6] REACTIONS OF YTTRIUM CARBON BONDS WITH ACTIVE HYDROGEN-CONTAINING MOLECULES - A USEFUL SYNTHETIC METHOD FOR PERMETHYLYTTROCENE DERIVATIVES [J].

DENHAAN, KH ;

WIELSTRA, Y ;

TEUBEN, JH .

ORGANOMETALLICS, 1987, 6 (10) :2053-2060

[7] ORGANOMETALLIC COMPOUNDS OF GROUP-III .41. DIRECT OBSERVATION OF THE INITIAL INSERTION OF AN UNSATURATED HYDROCARBON INTO THE TITANIUM CARBON BOND OF THE SOLUBLE ZIEGLER POLYMERIZATION CATALYST, CP2TICL2-MEALCL2 [J].

EISCH, JJ ;

PIOTROWSKI, AM ;

BROWNSTEIN, SK ;

GABE, EJ ;

LEE, FL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (24) :7219-7221

[8] REACTIONS OF VINYLZIRCONOCENE COMPLEXES WITH A ZIRCONIUM HYDRIDE - THE UNEXPECTED FORMATION OF [MU-(BETA-ETA-1-ALPHA,BETA-ETA-2-STYRYL] (MU-CHLORO)BIS[BIS(ETA-5-CYCLOPENTADIENYL)-ZIRCONIUM], A BINUCLEAR (OLEFIN)ZIRCONOCENE COMPLEX [J].

ERKER, G ;

KROPP, K ;

ATWOOD, JL ;

HUNTER, WE .

ORGANOMETALLICS, 1983, 2 (11) :1555-1561

[9] CPZR(ALLYL)3 - THE MOLECULAR-STRUCTURE OF A PI-DYNAMIC AND SIGMA-DYNAMIC ALLYL TRANSITION-METAL COMPLEX [J].

ERKER, G ;

BERG, K ;

ANGERMUND, K ;

KRUGER, C .

ORGANOMETALLICS, 1987, 6 (12) :2620-2621

[10] (S-TRANS-ETA-4-DIENE)ZIRCONOCENE COMPLEXES [J].

ERKER, G ;

WICHER, J ;

ENGEL, K ;

KRUGER, C .

CHEMISCHE BERICHTE-RECUEIL, 1982, 115 (10) :3300-3310

← 1 2 3 4 →