Publication

New insights into catalytic hydrogenation by phosphido-substituted triruthenium clusters: confirmation of intact cluster catalysis by parahydrogen NMR

2004
Journal Articles

Abstract

The phosphido-substituted triruthenium cluster Ru-3(CO)(9)(mu-H)(mu-PPh2) is shown to react with H-2 to form the trihydride cluster Ru-3(CO)(9)(H)(mu-H)(2)(mu-PPh2), which undergoes a number of re-arrangement reactions on heating to yield other phosphido-substituted triruthenium clusters. In the presence of alkyne substrates, heating the system leads to catalytic hydrogenation via CO loss and the formation of a Ru-3(eta(2)-PhC=CHPh)(CO)(8)(mu-H)(PHPh2) resting state, in a reaction affected by the polarity of the solvent. No mononuclear fragments are observed in the catalytic transformation, confirming directly that the phosphido ligand is able to exert a stabilising influence on the cluster core.

Official source

https://infoscience.epfl.ch/entities/publication/bd5a9b5e-9185-43d5-b52a-91e41695fdb1

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2004
Journal Articles

Abstract

Official source

https://infoscience.epfl.ch/entities/publication/bd5a9b5e-9185-43d5-b52a-91e41695fdb1

About this result

Related concepts (29)

Asymmetric hydrogenation

Asymmetric hydrogenation is a chemical reaction that adds two atoms of hydrogen to a target (substrate) molecule with three-dimensional spatial selectivity. Critically, this selectivity does not come from the target molecule itself, but from other reagents or catalysts present in the reaction. This allows spatial information (what chemists refer to as chirality) to transfer from one molecule to the target, forming the product as a single enantiomer.

Bridging ligand

In coordination chemistry, a bridging ligand is a ligand that connects two or more atoms, usually metal ions. The ligand may be atomic or polyatomic. Virtually all complex organic compounds can serve as bridging ligands, so the term is usually restricted to small ligands such as pseudohalides or to ligands that are specifically designed to link two metals. In naming a complex wherein a single atom bridges two metals, the bridging ligand is preceded by the Greek letter mu, μ, with a subscript number denoting the number of metals bound to the bridging ligand.

Transfer hydrogenation

In chemistry, transfer hydrogenation is a chemical reaction involving the addition of hydrogen to a compound from a source other than molecular . It is applied in laboratory and industrial organic synthesis to saturate organic compounds and reduce ketones to alcohols, and imines to amines. It avoids the need for high-pressure molecular used in conventional hydrogenation. Transfer hydrogenation usually occurs at mild temperature and pressure conditions using organic or organometallic catalysts, many of which are chiral, allowing efficient asymmetric synthesis.

Related publications (7)

New insights into catalytic hydrogenation by phosphido-substituted triruthenium clusters: confirmation of intact cluster catalysis by parahydrogen NMR

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