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.
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收藏
页码：251 / 255
页数：5
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