Diastereomeric half-sandwich Ru(II) cationic complexes containing amino amide ligands. Synthesis, solution properties, crystal structure and catalytic activity in transfer hydrogenation of acetophenone

被引：26

作者：

Bacchi, Alessia ^{[1
]}

Pelagatti, Paolo ^{[1
]}

Pelizzi, Corrado ^{[1
]}

Rogolino, Dominga ^{[1
]}

机构：

[1] Univ Parma, Dipartimento Chim Gen & Inorgan, I-43100 Parma, Italy

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2009年 / 694卷 / 19期

关键词：

Ruthenium; Amino amides; Chiral complexes; Configurational stability; Transfer hydrogenation; ESI; ASYMMETRIC TRANSFER-HYDROGENATION; BIOLOGICALLY IMPORTANT LIGANDS; RUTHENIUM(II) ARENE COMPLEXES; TRANSITION-METAL-COMPLEXES; BIFUNCTIONAL CATALYSIS; TRANSFER REDUCTION; AROMATIC KETONES; ALDOL REACTION; L-PROLINAMIDE; IRIDIUM(III);

D O I：

10.1016/j.jorganchem.2009.05.010

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The cationic complexes [(eta(6)-arene) Ru(N,O-amino amide) X]Y (arene = p-cymene or indane; N, O-amino amide = (L)-proline amide or (L)-phenylalanine amide; X = Cl or I; Y = Cl, I or PF6) have been synthesised and fully characterized by spectroscopic and analytical methods. In several cases (1a, 3a, 4a, 4b, 5) the metal configuration has been definitively established by X-ray analysis on single crystal. The lability of the metal center in solution has been studied by H-1 NMR and CD techniques. The highest configurational stability has been found in the complexes of the type [(eta(6)-indane)Ru(N,O-proline amide)Cl]Y (4a, b). The complexes 1b, 2a-b, 3b, 4b and 5 are good precatalysts for the transfer hydrogenation of acetophenone in basic i-PrOH, with ee up to 76% at 30 degrees C. An ESI(+)-MS study of pre-catalytic solutions has provided useful information on the catalytic mechanism. (C) 2009 Elsevier B. V. All rights reserved.

引用

页码：3200 / 3211

页数：12

共 59 条

[51] Amino alcohol effects on the ruthenium(II)-catalysed asymmetric transfer hydrogenation of ketones in propan-2-ol [J].