Ruthenium(III) complexes of amine-bis(phenolate) ligands as catalysts for transfer hydrogenation of ketones

Kannan S; Kumar KN; Ramesh R

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Ruthenium(III) complexes of amine-bis(phenolate) ligands as catalysts for transfer hydrogenation of ketones

机译：胺-双（酚盐）配体的钌（III）配合物作为酮转移加氢的催化剂

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Twelve ruthenium(III) complexes bearing amine-bis(phenolate) tripodal ligands of general formula [Ru(L-1-L-3)(X)(EPh3)(2)] (where L-1-L-3 are dianionic tridentate chelator) have been synthesized by the reaction of ruthenium(III) precursors [RuX3(EPh3)(3)] (where E = P, X = Cl; E = As, X = Cl or Br) and [RuBr3(PPh3)(2)(CH3OH)] with the tripodal tridentate ligands H2L1, H2L2 and H2L3 in benzene in 1:1 molar ratio. The newly synthesized complexes have been characterized by analytical (elemental and magnetic susceptibility) and spectral methods. The complexes are one electron paramagnetic (low-spin, d(5)) in nature. The EPR spectra of the powdered samples at RT and the liquid samples at LNT shows the presence of three different 'g' values (g(x) not equal g(y) not equal g(z)) indicate a rhombic distortion around the ruthenium ion. The redox potentials indicate that all the complexes undergo one electron transfer process. The catalytic activity of one of the complexes [Ru(pcr-chx)Br(AsPh3)(2)] was examined in the transfer hydrogenation of ketones and was found to be efficient with conversion up to 99% in the presence of isopropanol/KOH. (c) 2007 Elsevier Ltd. All rights reserved.

机译：十二个带有通式[Ru（L-1-L-3）（X）（EPh3）（2）]的胺-双（酚盐）三脚架配体的钌（III）配合物（其中L-1-L-3为双阴离子三齿螯合剂）是通过钌（III）前体[RuX3（EPh3）（3）]（其中E = P，X = Cl; E = As，X = Cl或Br）和[RuBr3（PPh3）（2）（CH3OH）]在苯中的三脚架三齿配体H2L1，H2L2和H2L3摩尔比为1：1。新合成的配合物已通过分析（元素和磁化率）和光谱方法进行了表征。该络合物本质上是一种顺磁性电子（低自旋，d（5））。粉末状样品在室温和LNT处的EPR光谱显示存在三个不同的'g'值（g（x）不等于g（y）不等于g（z））表明钌周围的菱形畸变离子。氧化还原电势表明所有配合物都经历一个电子转移过程。在酮的转移氢化中检查了其中一种配合物[Ru（pcr-chx）Br（AsPh3）（2）]的催化活性，发现在异丙醇/ KOH存在下，其转化率高达99％时是有效的。。（c）2007 Elsevier Ltd.保留所有权利。

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《Polyhedron: The International Journal for Inorganic and Organometallic Chemistry》 |2008年第2期|共8页
作者
Kannan S; Kumar KN; Ramesh R;
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正文语种 eng
中图分类化学;
关键词
synthesis; ruthenium(III); symmetrical tripodal chelator; characterization; catalytic transfer hydrogenation; ASYMMETRIC TRANSFER HYDROGENATION; SCHIFF-BASE COMPLEXES; ENANTIOSELECTIVE HYDROGENATION; STEREOSELECTIVE HYDROGENATION; SELECTIVE HYDROGENATION; CARBONYL-COMPOUNDS; PHOSPHINE-LIGANDS; AROMATIC KETONES; HIGHLY EFFICIENT; TRIPODAL LIGANDS;

机译：合成;钌（III）;对称的三脚形螯合剂;表征;催化转移加氢;不对称转移加氢;席夫夫基配合物;对映选择性加氢;立体选择性加氢;选择性加氢;羰基缩醛;磷酸酯脂类;

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专利

1. Ruthenium(III) complexes of amine-bis(phenolate) ligands as catalysts for transfer hydrogenation of ketones [J] . Kannan S, Kumar KN, Ramesh R Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 2008,第2期

机译：胺-双（酚盐）配体的钌（III）配合物作为酮转移加氢的催化剂
2. Effect of ligand modification on hydrogen production catalyzed by iron (III) complexes supported by amine-bis(phenolate) ligands [J] . Tang Ling-Zhi, Lin Chen-Neng, Zhan Shu-Zhong Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 2016,第Null期

机译：胺-双（酚盐）配体负载的铁（III）配合物催化配体修饰对产氢的影响
3. Effect of ligand modification on hydrogen production catalyzed by iron (III) complexes supported by amine-bis(phenolate) ligands [J] . Tang Ling-Zhi, Lin Chen-Neng, Zhan Shu-Zhong Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 2016,第Null期

机译：胺-双（酚盐）配体负载的铁（III）配合物催化配体修饰对产氢的影响
4. Effective Asymmetric Transfer Hydrogenation of Ketones Catalyzed by A New Chiral P-N-P Ligand-Ruthenium Complexes [C] . Yoji Oderaotoshi, Yuki Noguchi, Satoshi Minakata Symposium on Organometallic Chemistry . 2006

机译：新的手性P-N-P配体 - 钌配合物催化的酮催化的有效不对称转移氢化
5. I. Stereochemistry of cyclopropane formation involving group (IV) organometallic complexes. II. Slower stoichiometric and faster catalytic reduction of aldehydes by the PPh(3) substituted hydroxycyclopentadienyl ruthenium hydride [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COH)]Ru(CO)(PPh(3))H: A highly chemoselective catalyst for hydrogenation of aldehydes over ketones. [D] . Strotman, Neil Adham. 2005

机译：I.涉及（IV）族有机金属配合物的环丙烷形成的立体化学。二。由PPh（3）取代的羟基环戊二烯基氢化钌[2,5-Ph（2）-3,4-Tol（2）（eta（5）-C（4）COH）] Ru的化学计量较慢和较快的醛催化还原（CO）（PPh（3））H：一种高度化学选择性的催化剂，用于醛在酮上的氢化。
6. Aminotriazole Mn(I) Complexes as Effective Catalysts for Transfer Hydrogenation of Ketones [O] . Dr. Oriol Martínez‐Ferraté, Dr. Christophe Werlé, Dr. Giancarlo Franciò, -1

机译：氨基三唑Mn（I）配合物作为有效的酮转移加氢催化剂
7. Ruthenium(II) complex catalysts bearing a 2,6-bis(tetrazolyl)pyridine ligand for the transfer hydrogenation of ketones [O] . Liandi Wang, Tingting Liu 2018

机译：钌（II）含有2,6-双（四唑基）吡啶配体的复合催化剂，用于转移酮的酮氢化
8. Kinetic study on the adsorption and reaction of hydrogen over silica-supported ruthenium and silver-ruthenium catalysts during the hydrogenation of carbon monoxide [R] . VanderWiel, D. P. 1999

机译：二氧化碳加氢过程中二氧化硅负载钌和银 - 钌催化剂上氢的吸附和反应动力学研究

Ruthenium(III) complexes of amine-bis(phenolate) ligands as catalysts for transfer hydrogenation of ketones

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