Disilametallacyclic chemistry for efficient catalysis
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 o...
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| Published in | Dalton transactions : an international journal of inorganic chemistry Vol. 46; no. 24; pp. 7644 - 7655 |
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| Main Authors | , |
| Format | Journal Article |
| Language | English |
| Published |
England
20.06.2017
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| Subjects | |
| Online Access | Get full text |
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| Summary: | 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.
Disilametallacyclic species of late transition metals behave as key intermediates for efficient catalytic reactions proceeding through new mechanisms. |
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| Bibliography: | Yusuke Sunada received his B.S. (1999) and Ph.D. (2004) degrees from Nagoya University under the supervision of Professor Kazuyuki Tatsumi. He was appointed as an Assistant Professor at Kyushu University, Institute for Materials Chemistry and Engineering, in 2004, working with Professor Hideo Nagashima. In 2016, he moved to the University of Tokyo as an Associate Professor. His research interest includes the design and synthesis of highly reactive organometallic complexes and clusters. He received the Japan Society of Coordination Chemistry (JSCC) Award for Young Chemists (2015) and the Young Scientist Award of the Society of Silicon Chemistry, Japan (2013). Hideo Nagashima received his B.S. (1977), M.E. (1979) and D. Eng. degrees from the Tokyo Institute of Technology under the supervision of Professor Jiro Tsuji (Dr Palladium). He joined the faculty of the Toyohashi University of Technology in 1982 and was a research associate of Prof. Charles P. Casey at the University of Madison, Wisconsin, during 1985 and 1986. He was promoted as a professor at Kyushu University in 1997. His research interest is organometallic chemistry and catalysis, in particular, preparation of organometallic complexes with unique structures and their applications to practically useful organic and polymer synthesis. ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c7dt01275f |