THE 1ST MEASUREMENTS OF ACTIVATION VOLUMES FOR HYDRIDE FLUXIONALITY ON METAL-CLUSTERS - INTRAMOLECULAR EXCHANGE OF HYDRIDES ON H(MU-H)OS3(CO)10(PPH3) AND (MU-H)2RU3(MU-3-CHCO2ME)(CO)9

被引：20

作者：

KEISTER, JB ^{[1
]}

FREY, U ^{[1
]}

ZBINDEN, D ^{[1
]}

MERBACH, AE ^{[1
]}

机构：

[1] UNIV LAUSANNE,INST CHIM MINERALE & ANALYT,CH-1005 LAUSANNE,SWITZERLAND

来源：

ORGANOMETALLICS | 1991年 / 10卷 / 05期

关键词：

D O I：

10.1021/om00051a046

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The first volumes of activation for hydride fluxionality on transition-metal clusters have been determined by analysis of H-1 NMR line shapes recorded at pressures up to 200 MPa. For exchange of the two bridging hydrides of (mu-H)2Ru3(mu-3-CHCO2Me)(CO)9 the value for DELTA V-doubled-ended-dagger of + 4.1 (+/- 0.3) cm3/mol is consistent with an exchange pathway involving migration of one hydride from a doubly bridging coordination mode to a terminal coordination site in the transition state. For exchange of bridging and terminal hydride ligands of H(mu-H)Os3(CO)10(PPh3) the value for DELTA V-double-ended-dagger of -0.8 (+/- 0.4) cm3/mol is consistent with a transition state in which both hydrides are bridging.

引用

页码：1497 / 1501

页数：5

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