- Regioselective Hydrosilylation of Olefins Catalyzed by a Molecular Calcium Hydride Cation
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Chemo- and regioselectivity are often difficult to control during olefin hydrosilylation catalyzed by d- and f-block metal complexes. The cationic hydride of calcium [CaH]+ stabilized by an NNNN macrocycle was found to catalyze the regioselective hydrosilylation of aliphatic olefins to give anti-Markovnikov products, while aryl-substituted olefins were hydrosilyated with Markovnikov regioselectivity. Ethylene was efficiently hydrosilylated by primary and secondary hydrosilanes to give di- and monoethylated silanes. Aliphatic hydrosilanes were preferred over other commonly employed hydrosilanes: Arylsilanes such as PhSiH3 underwent scrambling reactions promoted by the nucleophilic hydride, while alkoxy- and siloxy-substituted hydrosilanes gave isolable alkoxy and siloxy calcium derivatives.
- Schuhknecht, Danny,Spaniol, Thomas P.,Maron, Laurent,Okuda, Jun
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supporting information
p. 310 - 314
(2019/11/26)
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- Olefin hydrosilylation catalyzed by cationic nickel(II) allyl complexes: A non-innocent allyl ligand-assisted mechanism
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The arene-supported cationic nickel allyl complexes serve as good catalysts for olefin hydrosilylation at room temperature. Detailed mechanistic studies based on experiments and DFT calculations support the novel mechanism, which includes the facile Si-H bond cleavage and Si-C bond formation, assisted by a non-innocent allyl ligand.
- Mathew,Nakajima,Choe,Urabe,Ando,Sato,Shimada
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supporting information
p. 6723 - 6726
(2016/06/01)
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- SATURATED AND UNSATURATED SILAHYDROCARBONS VIA IRON AND COBALT PYRIDINE DIIMINE CATALYZED OLEFIN SILYLATION
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The present invention relates to processes for the synthesis of saturated and unsaturated silahydrocarbons using iron-containing or cobalt-containing catalysts. The processes of the invention can produce tetraalkylsilanes, phenyltrialkylsilanes, substituted phenyltrialkylsilanes and their mixtures, which are useful as lubricants and hydraulic fluids, as well as alkyl alkenylsilanes, phenyl alkenylsilanes and substituted phenyl alkenylsilanes and their mixtures, which are useful in the synthesis of saturated silahydrocarbons and other organofunctional silanes.
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Paragraph 0122; 0123; 0124
(2014/11/13)
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