Hydrosilylation of carbonyl compounds catalysed by ruthenium complexes

Eaborn, Colin; Odell, Kevin J.; Pidcock, Alan

doi:10.1016/s0022-328x(73)80022-1

Cited by 40 publications

(8 citation statements)

References 8 publications

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“…The NMR analyses demonstrated that the hydrosilylation reaction between ester group and SiH is possible. In literature, Bonnet et al obtained a yield of 60 mol% of the expected products after 250 min at 100 °C, for octyl acetate, but they also demonstrated that the addition reaction rate depends on the nature of the each ester structure and on the reaction temperature . In the present case, at 100 °C, more than 30 mol% of the expected structure is reached after 250 min of reaction.…”

Section: Resultssupporting

confidence: 58%

Polybutylene terephthalate reactive blending with polymethylhydrosiloxane by ruthenium‐catalyzed carbonyl hydrosilylation reaction

Cassagnau

Cruz-Boisson

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Carbonyl hydrosilylation reaction was developed to prepare reactive blending between PBT and polymethylhydrosiloxane (PMHS). It focused on the addition reaction of Si–H groups from PMHS onto carbonyl groups from PBT catalyzed by triruthenium dodecacarbonyl (Ru3(CO)12). An approach on PBT model compounds was carried out and investigated by NMR spectroscopy to evidence the potentiality and efficiency of carbonyl hydrosilylation reaction. At temperatures up to 100 °C, the hydrosilylation reaction can reach 33 mol% conversion in a few hours. Side reactions were also highlighted. Such side reactions can reach more than 23 mol% of the final products when temperature increases to 180 °C. Then hydrosilylation reaction was extended to PBT modification with a molar ratio of ester group/SiH = 3.5 and viscosity ratio polysiloxane/PBT = 4.0 × 10−5. The reaction was carried out in an internal mixer at 220 °C and followed through the evolution of the torque of the reactional medium. Samples for different processing times were investigated by SEM and rheology. From these analyses, the dispersion of PMHS was promoted with diameters of few micrometers. The elastic behavior of final material was characteristic of solid or gel‐like structures, suggesting a network structure formation consistent with the gel fraction increase from 0 to 0.55. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1855–1868

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Section: Resultssupporting

confidence: 58%

Polybutylene terephthalate reactive blending with polymethylhydrosiloxane by ruthenium‐catalyzed carbonyl hydrosilylation reaction

Cassagnau

Cruz-Boisson

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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“…The influence of the steric hindrance was underlined by Eaborn et al12 who described that hydrosilylation of aromatic aldehydes is markedly faster than hydrosilylation of aromatic ketones in the presence of RuCl 2 (PPh 3 ) 3 . Igarashi et al16 showed that hydrosilylation reaction of sterically hindered esters such as tert ‐butyl ester or five‐membered lactone gave moderate yields of the expected products (less than 45 mol %).…”

Section: Resultsmentioning

confidence: 99%

“…Transition‐metal salts and complexes catalysts were described as very efficient catalysts for the hydrosilylation reaction. For example, Eaborn et al12 compared the catalytic efficiency of ruthenium and rhodium complexes and more precisely RuCl 2 (PPh 3 ) 3 and RhCl(PPh 3 ) 3 . They reported that silylethers are successfully obtained from aliphatic ketone with the ruthenium complexes.…”

Section: Introductionmentioning

confidence: 99%

Efficient carbonyl hydrosilylation reaction: Toward EVA copolymer crosslinking

Bonnet

Bounor‐Legaré

Boisson

et al. 2011

J. Polym. Sci. A Polym. Chem.

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In this article, the hydrosilylation reaction of carbonyl groups of acetate derivatives and SiH groups of hydride‐terminated polydimethylsiloxane at high temperature (100–130 °C) are described. Triruthenium dodecacarbonyl, Ru3(CO)12, was used as effective catalyst for hydrosilylation reaction. The hydrosilylation reactions with octyl acetate and 4‐heptyl acetate were investigated by multinuclear NMR spectroscopy (1H, 13C, and 29Si). This work provides evidence of the addition reaction of SiH groups onto carbonyl groups. The influence of the nature of the acetate structure on the reaction kinetics was shown and the slight contribution of side reactions at high temperature highlighted. Hydrosilylation reaction was extent to the crosslinking of ethylene‐vinyl acetate (EVA) copolymer in the same range of temperature. The formation of EVA chemical network was demonstrated by HR‐MAS NMR spectroscopy and by measuring the gel fraction of EVA chains in hot toluene. From Flory theory, the crosslinking density of elastic strand was calculated to be 80 mol m−3 in agreement with the measurements from swelling ratio (VA/SiH molar ratio: 11.8). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

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“…On the other hand, while the transition-metal-catalyzed hydrosilation reactions between ketones or aldehydes and silanes to yield silyl ethers have been known for more than twenty-five years, they have not been applied in polymer synthesis. While nickel was the first catalyst reported for this reaction in monomer systems, 8 more recently tris(triphenylphosphine)rhodium chloride or tris(triphenylphosphine)ruthenium dichloride catalysts have been used. − Tris(triphenylphosphine)ruthenium dichloride is less effective 11 unless it is activated by addition of an equimolar amount of silver trifluoroacetate . The reason the rhodium- or ruthenium-catalyzed hydrosilation reactions have not been applied to polymer synthesis is not obvious.…”

Section: Introductionmentioning

confidence: 99%