INSERTION OF A VINYLIDENE UNIT INTO A RU-O BOND - SYNTHESIS AND MOLECULAR-STRUCTURE OF [C5H5(PPH3)RUC(=CHCO2ME)OC(ME)O]1

被引：38

作者：

DANIEL, T ^{[1
]}

MAHR, N ^{[1
]}

BRAUN, T ^{[1
]}

WERNER, H ^{[1
]}

机构：

[1] UNIV WURZBURG,INST ANORGAN CHEM,HUBLAND,W-8700 WURZBURG,GERMANY

来源：

ORGANOMETALLICS | 1993年 / 12卷 / 04期

关键词：

D O I：

10.1021/om00028a080

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The cyclopentadienyl ruthenium acetate [C5H5Ru(eta2-O2CMe)(PPh3)] (2) which is obtained on treatment of [C5H5Ru(eta3-2-MeC3H4)(PPh3)] (1) with acetic acid reacts with CO to give the carbonyl complex [C5H5Ru(CO)(PPh3)(eta1-O2CMe)] (3). In contrast, with HC=CCO2Me the cyclic vinyl ester ruthenium compound [C5H5(PPh3)RuC(=CHCO2Me) OC(Me)O] (4) instead of the expected vinylidene complex is formed. The X-ray crystal structure analysis (monoclinic space group C2c (No. 15) with a = 21.123(8) angstrom, b = 22.541(4) angstrom, c = 12.435(6) angstrom, and beta = 115.83(1)-degrees) reveals that the RuC(=CHCO2Me)OC(Me)O unit represents an intermediate state between a five-membered chelate ring and a separated Ru(=C=CHCO2Me)(eta1-O2CMe) moiety. From NMR measurements at various temperatures, it can be concluded that in solution a rapid Z/E isomerization at the exocyclic C=C bond of the chelate ligand of 4 takes place.

引用

页码：1475 / 1477

页数：3

共 22 条

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