Disilametallacyclic chemistry for efficient catalysis

Yusuke Sunada, Hideo Nagashima

Research output: Contribution to journalReview article

12 Citations (Scopus)

Abstract

This article discusses two new features of disilametallacyclic chemistry that contribute to the development of efficient catalytic reactions in organic synthesis. The first is disilametallacyclic intermediates in the hydrosilane reduction of carbonyl compounds. Experimental and theoretical studies on disilaplatinacycles suggested that the H 2 Pt(iv)Si 2 species generated by oxidative addition of 1,2-bis(dimethylsilyl)benzene behaves as a highly reactive hydride to reduce amides to amines. This mechanism via disilametallacyclic intermediates explains the efficient hydrosilane reduction of carbonyl compounds with α,ω-bifunctional hydrosilanes catalyzed by other transition metals. The second is hydrogenation of alkenes by disilaferra- or disilaruthenacyclic complexes as catalyst precursors. A new mechanism not involving the conventional oxidative addition of H 2 was suggested from DFT calculations, in which activation of the H-H bond occurs in the metal-silicon bond of the disilametallacyclic intermediate. Disilametallacyclic intermediates contribute to efficient catalytic reactions through this σ-CAM (σ-complex assisted mechanism) type mechanism.

Original languageEnglish
Pages (from-to)7644-7655
Number of pages12
JournalDalton Transactions
Volume46
Issue number24
DOIs
Publication statusPublished - Jan 1 2017

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Carbonyl compounds
Catalysis
Alkenes
Silicon
Benzene
Discrete Fourier transforms
Amides
Hydrides
Hydrogenation
Amines
Transition metals
Metals
Chemical activation
Catalysts

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Disilametallacyclic chemistry for efficient catalysis. / Sunada, Yusuke; Nagashima, Hideo.

In: Dalton Transactions, Vol. 46, No. 24, 01.01.2017, p. 7644-7655.

Research output: Contribution to journalReview article

Sunada, Yusuke ; Nagashima, Hideo. / Disilametallacyclic chemistry for efficient catalysis. In: Dalton Transactions. 2017 ; Vol. 46, No. 24. pp. 7644-7655.
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