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Hydrosilylation is an important process, not only in the silicon industry to produce silicon polymers, but also in fine chemistry. In this review, the development of rhenium-based catalysts for the hydrosilylation of unsaturated bonds in carbonyl-, cyano-, nitro-, carboxylic acid derivatives and alkenes is summarized. Mechanisms of rhenium-catalyzed hydrosilylation are discussed. 相似文献
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Guillaume Tintori Pierre Nabokoff Ruqaya Buhaibeh Dr. David Bergé‐Lefranc Dr. Sébastien Redon Dr. Julie Broggi Prof. Patrice Vanelle 《Angewandte Chemie (International ed. in English)》2018,57(12):3148-3153
Organic electron donors (OEDs) are powerful reducing agents recognized for their potential in the reduction of challenging substrates and in original applications. Nonetheless, their low stability in atmospheric oxygen or over time complicates their manipulation and storage. To overcome these constraints and enhance OED practicality, new air‐ and moisture‐stable aminopyridinium carboxylate and carbonate precursors were synthesized and thermally activated to generate the potent electron donor in situ. Carboxylate adducts proved to be excellent latent OED systems, enabling the facile and efficient reduction of challenging substrates. Their reduction properties were correlated to their structural characteristics by thermogravimetric and spectroscopic analysis. 相似文献
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Ruqaya Buhaibeh Oleg A. Filippov Antoine Bruneau‐Voisine Jrmy Willot Carine Duhayon Dmitry A. Valyaev Noël Lugan Yves Canac Jean‐Baptiste Sortais 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(20):6799-6803
Deprotonation of the MnI NHC‐phosphine complex fac‐[MnBr(CO)3(κ2P,C‐Ph2PCH2NHC)] ( 2 ) under a H2 atmosphere readily gives the hydride fac‐[MnH(CO)3(κ2P,C‐Ph2PCH2NHC)] ( 3 ) via the intermediacy of the highly reactive 18‐e NHC‐phosphinomethanide complex fac‐[Mn(CO)3(κ3P,C,C‐Ph2PCHNHC)] ( 6 a ). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16‐e mangana‐substituted phosphonium ylide complex fac‐[Mn(CO)3(κ2P,C‐Ph2P=CHNHC)] ( 6 b ) as key intermediate able to activate H2 via a non‐classical mode of metal‐ligand cooperation implying a formal λ5‐P–λ3‐P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre‐catalysts for ketone hydrogenation in the MnI series reported to date (TON up to 6200). 相似文献
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