UNPRECEDENTED METATHESIS OF METAL-CARBON AND CARBON-CARBON BONDS IN ALPHA-AGOSTIC N-ALKYL NIOBIUM ALKYNE COMPLEXES

被引：21

作者：

ETIENNE, M

BIASOTTO, F

MATHIEU, R

机构：

来源：

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS | 1994年 / 14期

关键词：

D O I：

10.1039/c39940001661

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The alpha-agostic n-ethyl and n-propyl niobium alkyne complexes [NbL(Cl)(mu-H-CHR)(PhC=CR')] [L = hydridotris(3,5-dimethylpyrazolyl)borate; R = Me, Et; R' = Me, Et, Pr-n] undergo a thermolytic exchange of the niobium and alkyne-bound alkyl groups to give [NbL(Cl)(R')(PhC=CCH(2)R]; first-order kinetic parameters have been obtained when R = R' = Me (Delta H-double dagger = 113 kJ mol(-1), Delta S-double dagger = 4J K-1 mol(-1)).

引用

收藏

页码：1661 / 1662

页数：2

相关论文

共 12 条

[1] BETA-MIGRATORY INSERTION REACTIONS OF (ETA-5-C5R'5)RH(L)(C2H4)R+BF4- (R' = H, CH3 R = H, C2H5 L = P(OME)3, PME3) - COMPARISON OF THE ENERGETICS OF HYDRIDE VERSUS ALKYL MIGRATION [J].

BROOKHART, M ;

HAUPTMAN, E ;

LINCOLN, DM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (26) :10394-10401

[2]

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

[3] C-H ACTIVATION MECHANISMS AND REGIOSELECTIVITY IN THE CYCLOMETALATION REACTIONS OF BIS(PENTAMETHYLCYCLOPENTADIENYL)THORIUM DIALKYL COMPLEXES [J].

BRUNO, JW ;

SMITH, GM ;

MARKS, TJ ;

FAIR, CK ;

SCHULTZ, AJ ;

WILLIAMS, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (01) :40-56

[4] KINETICS AND MECHANISM OF THE INSERTION OF OLEFINS INTO NIOBIUM-HYDRIDE AND TANTALUM-HYDRIDE BONDS - A STUDY OF THE COMPETITION BETWEEN STERIC AND ELECTRONIC EFFECTS [J].

BURGER, BJ ;

SANTARSIERO, BD ;

TRIMMER, MS ;

BERCAW, JE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (10) :3134-3146

[5]

COLLMAN JP, 1987, PRINCIPLES APPLICATI

[6] STERIC AND ELECTRONIC PROBES FOR ALPHA-AGOSTIC INTERACTION IN A NIOBIUM ETHYL COMPLEX [J].

ETIENNE, M .

ORGANOMETALLICS, 1994, 13 (02) :410-412

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

GREEN, MLH ;

SELLA, A ;

WONG, LL .

ORGANOMETALLICS, 1992, 11 (07) :2650-2659

[8]

JORDAN RF, 1991, ADV ORGANOMET CHEM, V32, P325

[9] ISOTOPE EFFECTS ASSOCIATED WITH ALPHA-OLEFIN INSERTION IN ZIRCONOCENE-BASED POLYMERIZATION CATALYSTS - EVIDENCE FOR AN ALPHA-AGOSTIC TRANSITION-STATE [J].

KRAULEDAT, H ;

BRINTZINGER, HH .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1990, 29 (12) :1412-1413

[10] ALPHA-AGOSTIC ASSISTANCE IN ZIEGLER-NATTA POLYMERIZATION OF OLEFINS - DEUTERIUM ISOTOPIC PERTURBATION OF STEREOCHEMISTRY INDICATING COORDINATION OF AN ALPHA-C-H BOND IN CHAIN PROPAGATION [J].

PIERS, WE ;

BERCAW, JE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (25) :9406-9407