Activation of Linear Alkanes by a Hydrido Triruthenium Cluster and Associated Skeletal Rearrangements

Bulletin of the Chemical Society of Japan - Tập 87 Số 4 - Trang 443-458 - 2014
Toshiro Takao1, Hiroharu Suzuki1
1Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology

Tóm tắt

Abstract We explored polyhydrido cluster reaction chemistry for over two decades, developing rational syntheses of di-, tri-, tetra-, and pentanuclear clusters of ruthenium. In our study of cluster chemistry, we found that triruthenium pentahydrido complex [{Cp*Ru(µ-H)}3(µ3-H)2] (1) (Cp*: η5-C5Me5) reacts with linear alkanes to exclusively afford a closo-ruthenacyclopentadiene complex 2. The reaction mechanism has been elucidated by the isolation and alternative preparation of several important intermediates by the reaction of 1 with other hydrocarbons, such as alkynes, dienes, and alkenes. The mechanism is shown to consist of two reversible and four irreversible steps involving dihydrogen elimination, where the cooperative interaction of neighboring metal centers with hydrocarbons on the cluster is clearly seen. Facile migration of a hydride from a metal center to the carbon atom is also observed during the reaction, which emphasizes the crucial role of hydrido ligands in the skeletal rearrangement of hydrocarbyl ligands on a polyhydrido cluster. In addition, coupling reaction between two hydrocarbyl ligands placed on each face of the triruthenium core with concomitant partial cleavage of the cluster skeleton has also been observed. Such a flexible cluster skeleton enables unusual transformation of hydrocarbons on the cluster.

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Bulletin of the Chemical Society of Japan

Tập 87 Số 4

443-458

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