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Relevant academic research and scientific papers

An air-stable, Zn2+-based catalyst for hydrosilylation of alkenes and alkynes

Hydrosilylation of C-C double and C-C triple bonds is one of the most widely used processes in organosilicon chemistry, mostly catalyzed by Pt-based complexes. We report here the synthesis of an air-stable dicationic Zn2+-based complex in a hem

Carbonyl and olefin hydrosilylation mediated by an air-stable phosphorus(iii) dication under mild conditions

The readily-accessible, air-stable Lewis acid [(terpy)PPh][B(C6F5)4]21 is shown to mediate the hydrosilylation of aldehydes, ketones, and olefins. The utility and mechanism of these hydrosilylations are considered.

Silicon(II) Cation Cp*Si:+ X-: A New Class of Efficient Catalysts in Organosilicon Chemistry

The catalytic activity of the pentamethylcyclopentadienylsilicon(II) cation Cp*Si:+ was investigated. It was shown that Cp*Si:+ efficiently catalyzes reactions of technical relevance in organosilicon chemistry: Cp*Si:+ proved to be a very efficient nonmetallic catalyst for the hydrosilylation of olefins at low catalyst amounts of 0.01 mol % and for the Piers-Rubinsztajn reaction in order to make controlled silicone topologies. The thermal induction of hydrosilylation which is important for the manufacturing of silicone rubber can be achieved by small amounts of alkoxysilanes.

Hydrosilylation of olefins catalyzed by well-Defined cationic aluminum complexes: Lewis acid versus insertion mechanisms

The cationic aluminum complex [NacNacAlH]+ (2; NacNac = CH{C(Me)N(2,6-Pri2C6H3)}2) can be easily generated from NacNacAlH2 by hydride abstraction and functions as a catalyst for the hydrosilylation of olefins and alkynes. Mechanistic studies suggest that, although olefin insertion into the Al?H bond is very facile, the catalysis does not proceed by an insertion/metathesis mechanism but likely by Lewis acid activation. Stoichiometric reactions of 2 with alkynes furnished unexpected products of CC addition across the NacNacAl moiety to give tripodal aluminum cations, which are also potent catalysts for the hydrosilylation of alkynes.

The highly lewis acidic dicationic phosphonium salt: [(SIMes)PFPh 2][B(C6F5)4]2

The dicationic imidazolium-phosphonium salt [(SIMes)PFPh 2][B(C6F5)4]2 has been prepared and shown to exhibit remarkable Lewis acidity in stoichiometric reactions and acting as an effective Lewis acid catalyst for the hydrodefluorination of fluoroalkanes and the hydrosilylation of olefins.

Olefin isomerization and hydrosilylation catalysis by lewis acidic organofluorophosphonium salts

Organofluorophosphonium salts of the formula [(C6F 5)3-xPhxPF][B(C6F5) 4] (x = 0, 1) exhibit Lewis acidity derived from a low-lying σ* orbital at P opposite F. This acidity is evidenced by the reactions of these salts with olefins, which catalyze the rapid isomerization of 1-hexene to 2-hexene, the cationic polymerization of isobutylene, and the Friedel-Crafts-type dimerization of 1,1-diphenylethylene. In the presence of hydrosilanes, olefins and alkynes undergo efficient hydrosilylation catalysis to the alkylsilanes. Experimental and computational considerations of the mechanism are consistent with the sequential activation and 1,2-addition of hydrosilane across the unsaturated C-C bonds.

Cationic ethylzinc compound: A benzene complex with catalytic activity in hydroamination and hydrosilylation reactions

The tight ion pair [EtZn(η3-C6H 6)][CHB11Cl11]?C6H6 (1?C6H6) was obtained through β-hydrogen abstraction and concomitant ethene elimination from Et2Zn with the trityl salt [Ph3C][CHB11Cl11]. This ionlike species shows catalytic activity in hydrosilylation and intramolecular hydroamination reactions. The amine adduct {CH2CHCH 2C(Ph2)CH2NH2}3ZnCB 11Cl11 (3), which features a rare transition metal-carborane σ bond, was isolated from a hydroamination experiment.

Mechanistic studies of palladium(II)-catalyzed hydrosilation and dehydrogenative silation reactions

The cationic Pd(II) complexes, [(phen)Pd(CH3)(L)]+[BAr'4]- phen = 1,10-phenanthroline; L = Et2O, Me3SiC≡CSiMe3; Ar' = 3,5-(CF3)2C6H3) catalyze the hydrosilation and dehydrogenative silation of olefins. Hydrosilation of ethylene, tert-butylethylene, 1-hexene, and cyclohexene by HSiR3 (R = CH2CH3, C6H5) occurs in the presence of 1 mol% [(phen)Pd(CH3)(L)]+[BAr'4]-. The reaction of tert-butylethylene with HSi(i-Pr)3 in the presence of [(phen)Pd(CH3)(L)]+[BAr'4]- yields neohexane and t-BuCH=CHSi(i-Pr)3. Low-temperature NMR experiments revealed that the catalyst resting state for the silations of ethylene and alkyl-substituted olefins is [(phen)Pd(SiR3)(η2-H2C=CHR')]+[BAr'4]-. Evidence for rapid, reversible silyl migration at -70°C was observed by 1H NMR spectroscopy. Deuterium labeling studies show that the intermediate Pd(II) alkyl complexes can isomerize via a series of β-hydride eliminations followed by reinsertions of olefin prior to reaction with DSiEt3. Styrene undergoes both hydrosilation and dehydrogenative silation in the presence of [(phen)Pd(CH3)(L)]+[BAr'4]- or [(phen)Pd(η3-CH(CH3)C6H5)]+[BAr'4]- yielding ethylbenzene, R3SiCH2CH2C6H5 and trans-R3SiCH=CHPh (R = CH2CH3, CH(CH3)2). 1H NMR spectroscopy revealed that the π-benzyl complexes [(phen)Pd(η3-CH(CH2SiR3)C6H5)]+[BAr'4]- and [(phen)Pd(η3-CH(CH3)C6H5)]+[BAr'4]- are the catalyst resting states for the silation reactions of styrene.

Alkane Functionalization on a Preparative Scale by Mercury-Photosensitized Cross-Dehydrodimerization

Alkanes can be functionalized with high conversions and in high chemical and quantum yields on a multigram scale by mercury-photosensitized reaction between an alkane and alcohols, ethers, or silanes to give homodimers and cross-dehydrodimers.The separation of the product mixtures is often particulary easy because of a great difference in polarity of the homodimers and cross-dimers.It is also possible to bias the product composition when the ratio of the components in the vapor phase is adjusted by altering the liquid composition.This is useful either to maximize chemical yield or to ease separation by favoring the formation of the most easily separated pair of compounds.The mechanistic basis of the reaction is discussed and a number of specific types of syntheses, for example of 2,2-disubstituted carbinols, are described in detail.The selectivity of cross-dimerization is shown to exceed that for homodimerization and reasons are discussed.Relative reactivities of different compounds and classes of compound are MeOHp-dioxanecyclohexane1,3,5-trioxacyclohexaneethanolisobutaneTHFEt3SiH.The observed selectivities generally parallel those for homodimerization, reported in the preceding paper, but certain differences are noted, and reasons for the differences are proposed.The bond-dissociation energy of Et3SiH is estimated from the reactivity data to be 90 kcal/mol.Eleven new carbinols are synthesized.

Alkane Functionalisation on a Preparative Scale by Mercury Photosensitisation

Alkanes can be functionalised on a multigram scale by mercury photosensitised cross-dimerisation with alcohols, ethers and silanes.