Creation of Reactive Transition Metal Cyanocarbanions bearing Novel Catalytic Functions as a Substitute of Base

过渡金属氰基碳负离子是碳-碳键形成反应的重要中间体。发现C-和N-键合的氰基碳负离子配合物都可以有效地合成，并且可以通过改变金属中心、配体和α-取代基来控制它们在两种异构体之间的相互转化。光谱和动力学研究表明，异构化通过金属在腈配体的π-键上的分子内滑动机制进行。此外，通过化学计量反应和催化反应研究了一系列氮键合钌氰基碳负离子配合物对醛、酮、炔和腈的反应性。这些研究为我们以前开发的催化Aldol和Michael型反应的反应机理提供了重要信息。

Transition metal cyanocarbanions are important intermediates for carbon-carbon bond forming reactions. Both C- and N- bound cyanocarbanion complexes were found to be synthesized efficiently, and their interconversion between the two isomers can be controlled by changing a metal center, ligands, and α-substituted group. Spectroscopic and kinetic studies revealed that the isomerization undergoes via a mechanism which is intramolecular slipping of the metal throughout the π-bond of nitrile ligands. Furthermore, reactivities of a series of N- bound ruthenium cyanocarbanion complexes towards aldehydes, ketones, alkynes, and nitriles were investigated by stoichiometiric and catalytic reactions. These studies gave important information about the reaction mechanism of the catalytic Aldol and Michael type reaction, which were previously developed by us.