An unexpectedly stable chiral hydrido-solvent complex of Ru-II: A mechanistic link in the enantioselective hydrogenation of pyrones

被引：23

作者：

Currao, A ^{[1
]}

Feiken, N ^{[1
]}

Macchioni, A ^{[1
]}

Nesper, R ^{[1
]}

Pregosin, PS ^{[1
]}

Trabesinger, G ^{[1
]}

机构：

[1] ETH ZENTRUM,INORGAN CHEM LAB,CH-8092 ZURICH,SWITZERLAND

来源：

HELVETICA CHIMICA ACTA | 1996年 / 79卷 / 06期

关键词：

D O I：

10.1002/hlca.19960790608

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The ligand (6,6'-dimethoxybiphenyl-2,2'-diyl)bis[3,5-di(tert-butyl)phenylphosphine] (1) forms an unexpectedly stable hydrido-bis-solvento complex of composition [RuH(isopropanol)(2)(I)]BF4, (2) under the conditions used in the enantioselective hydrogenation of pyrones. The structure of 2, determined by X-ray diffraction, represents the first well-characterized chiral five-coordinate bis-phosphine ruthenium-hydride complex stable as a solvento complex, and provides a structural link in the enantioselective pyrone hydrogenation cycle catalyzed by [Ru(OAc)(2)(1)]. Using the arene complex [RuH(p-cymene)(1)]BF4 (3), the chiral pocket of coordinated 1 is shown to be relatively rigid, via NMR spectroscopy. This is reflected in restricted rotation about one of the four P-[3,5-di(tert-butyl)phenyl] P-C-ipso bonds at room temperature.

引用

页码：1587 / 1591

页数：5

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