Niobium/Rhodium Bimetallic Complexes: Synthesis, Structures, and Catalytic Hydrosilylation of Acetophenone and Benzaldehyde

Leelasubcharoen Somying; Zhizhko Pavel A.; Kuzmina Lyudmila G.; Churakov Andrei V.; Howard Judith A. K.; Nikonov Georgii I.

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Niobium/Rhodium Bimetallic Complexes: Synthesis, Structures, and Catalytic Hydrosilylation of Acetophenone and Benzaldehyde

机译：铌/铑双金属配合物：苯乙酮和苯甲醛的合成，结构和催化氢化硅烷化

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Reactions of new imido phosphido complex, Cp2Nb(=NBu')(PPh2) (1), with olefin complexes of rhodium afford two types of compounds. With [(mu-Cl)Rh(C2H4)(2)](2), an imido/phosphido-bridged complex, Cp(Cl)Nb(mu-NBu')(mu-PPh2)RhCp (2), characterized by NMR and X-ray diffraction, was prepared. Formation of 2 represents a rare example of a Cp/Cl exchange reaction in organometallic chemistry. When 1 reacts with [mu-Cl)Rh(COD)](2), the target phosphido-bridged bimetallic complex Cp2Nb(=NBu')(mu-PPh2)Rh(Cl)(COD) (4) is formed. The structure of this product was established by NMR and an X-ray diffraction study. Both 2 and 4 are catalyst procursors for hydrosilylation of benzaldehyde and acceptophenone. The activity of the neutral complex 4 exceeds that of the cation [Cp2Nb(NBu')(PPh2)Rh(COD)]+ derived from 4 by chloride anion abstraction.

机译：新的亚氨基磷酸酯络合物Cp2Nb（= NBu'）（PPh2）（1）与铑的烯烃络合物的反应提供了两种类型的化合物。带有[（mu-Cl）Rh（C2H4）（2）]（2）的亚氨基/磷酸桥连络合物Cp（Cl）Nb（mu-NBu'）（mu-PPh2）RhCp（2），其特征在于制备了NMR和X射线衍射。 2的形成代表有机金属化学中Cp / Cl交换反应的罕见例子。当1与[mu-Cl] Rh（COD）]（2）反应时，形成目标磷酸桥双金属配合物Cp2Nb（= NBu'）（mu-PPh2）Rh（Cl）（COD）（4）。该产物的结构通过NMR和X射线衍射研究确定。 2和4均为苯甲醛和苯甲酮氢化硅烷化的催化剂前体。中性配合物4的活性超过通过氯化物阴离子提取衍生自4的阳离子[Cp2Nb（NBu'）（PPh2）Rh（COD）] +的活性。

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《Organometallics》 |2009年第15期|共7页
作者
Leelasubcharoen Somying; Zhizhko Pavel A.; Kuzmina Lyudmila G.; Churakov Andrei V.; Howard Judith A. K.; Nikonov Georgii I.;
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正文语种 eng
中图分类 545B0014-1;
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BRIDGED HETEROBIMETALLIC COMPLEXES; TRANSITION-METAL-COMPLEXES; N-HETEROCYCLIC CARBENE; COORDINATION CHEMISTRY; ASYMMETRIC HYDROSILYLATION; RHODIUM COMPLEXES; H BONDS; LIGANDS; PHOSPHIDO; REACTIVITY;

机译：桥接杂多金属配合物;过渡金属配合物;N-杂环碳原子;配位化学;不对称加氢甲硅烷基化;铑配合物;H键;配体;磷酸;反应活性;

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1. Niobium/Rhodium Bimetallic Complexes: Synthesis, Structures, and Catalytic Hydrosilylation of Acetophenone and Benzaldehyde [J] . Leelasubcharoen Somying, Zhizhko Pavel A., Kuzmina Lyudmila G., Organometallics . 2009,第15期

机译：铌/铑双金属配合物：苯乙酮和苯甲醛的合成，结构和催化氢化硅烷化
2. Catalytic hydrosilylation of substituted acetophenones by 1,1,3,3-tetrametyldisiloxane with complexes rhodium (I) and platinum (II) [J] . Zuev VV, de Vekki DA Phosphorus, Sulfur, and Silicon and the Related Elements . 2005,第9期

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3. Synthesis and characterization of a 1,3-phenylene-bridged N-alkyl bis(benzimidazole) CCC-NHC pincer ligand precursor: Homobimetallic silver and rhodium complexes and the catalytic hydrosilylation of phenylacetylene [J] . Huckaba A.J., Hollis T.K., Howell T.O., Organometallics . 2013,第1期

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4. Synthesis of Rh(III) Complexes Having a Disilacyclic Skeleton, and Catalytic Hydrosilylation of Ketones [C] . Yusuke Sunada, Yoshiki Fujimura, Hideo Nagashima Symposium on Organometallic Chemistry . 2007

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Niobium/Rhodium Bimetallic Complexes: Synthesis, Structures, and Catalytic Hydrosilylation of Acetophenone and Benzaldehyde

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