Intramolecular hydrogen bonding in transition metal clusters:: NMR evidence for an Os-H•••H-S interaction in H(μ-H)Os3(CO)10(HSR) (R = ethyl, cyclopentyl)

被引：4

作者：

Aime, S ^{[1
]}

Chierotti, MR ^{[1
]}

Gobetto, R ^{[1
]}

Russo, A ^{[1
]}

Stchedroff, MJ ^{[1
]}

机构：

[1] Univ Turin, Dipartimento Chim Inorgan, I-10125 Turin, Italy

来源：

INORGANICA CHIMICA ACTA | 2003年 / 351卷

关键词：

unconventional hydrogen bond; cluster; osmium; thiol; NMR; T-1;

D O I：

10.1016/S0020-1693(03)00120-8

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reaction of H2Os3(CO)(10) with RSH (R = CH2CH3, cyclopentylthiol) at low temperatures in CD2Cl2 affords three H(mu-H)Os-3(CO)(10)(RSH) adducts, where, by the C-13 NMR carbonyl spectrum, it can be shown that the thiol ligand occupies an axial position. The presence of an intermolecular (MHHS)-H-... interaction in the main isomer has been determined by longitudinal relaxation time measurements. The isolation of the 14,14 dipolar contribution to the terminal hydride relaxation affords a value of 1.97 Angstrom for the 'unconventional' hydrogen-hydrogen interaction in H(mu-H)Os-3(CO)(10)(RSH) (R = cyclopentylthiol). An intramolecular proton transfer from the thiol ligand RSH to the terminal hydride, via a dihydrogen bonded species, ultimately losing an H, molecule. leading to the formation of the stable product (mu-H)Os-3(CO)(10)(mu-SR) is proposed. (C) 2003 Elsevier Science B.V. All rights reserved.

引用

页码：251 / 255

页数：5

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