H/D isotopic exchange on the surface of a triosmium carbonyl cluster

被引：9

作者：

Aime, S ^{[1
]}

Dastru, W ^{[1
]}

Gobetto, R ^{[1
]}

Krause, J ^{[1
]}

Matas, L ^{[1
]}

Viale, A ^{[1
]}

机构：

[1] UNIV GIRONA,DEPT QUIM,GIRONA 17071,SPAIN

来源：

ORGANOMETALLICS | 1996年 / 15卷 / 23期

关键词：

D O I：

10.1021/om960527d

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reactions of both Os-3(CO)(10)(NCCH3)(2) and Os-3(CO)(11)(NCCH3) with HD Or with a mixture of H-2/D-2 in chloroform solution at room temperature afford a mixture of H2Os3(CO)(10) (Ia), HDOs3(CO)(10) (Ib), and D2Os3(CO)(10) (Ic). The three isotopomers are also obtained by reacting H2Os3(CO)(10) with D-2. By measurement of the rates of disappearance of Ia in the latter reaction at four different temperatures, the thermodynamic parameters have been estimated (E(a) = 43.7 kJ/mol, Delta H-double dagger = 41.2 kJ/mol, Delta S-double dagger = -0.17 kJ/(mol K)). No H/D isotopic exchange has been observed after heating Ia and Ic in toluene for several hours. A mechanism involving the reversible oxidative addition and reductive elimination of molecular hydrogen on H2Os3(CO)(10) via the formation of a fluxional tetra(hydrido, deuterio) intermediate is proposed.

引用

页码：4967 / 4970

页数：4

共 28 条

[1]

ADAMS AD, 1982, COMPREHENSIVE ORGANO, P1025

[2] TRIOSMIUM CLUSTER COMPOUNDS CONTAINING ISOCYANIDE AND HYDRIDE LIGANDS - CRYSTAL AND MOLECULAR-STRUCTURES OF (MU-H)(H)OS3(CO)10(CN-T-C4H9) AND (MU-H)2OS3(CO)9(CN-T-C4H9) [J].