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Heterogeneous Inhibition of Homogeneous Reactions: Karstedt Catalyzed Hydrosilylation

Faglioni, Francesco and Blanco, Mario and Goddard, William A., III and Saunders, Dennis (2002) Heterogeneous Inhibition of Homogeneous Reactions: Karstedt Catalyzed Hydrosilylation. Journal of Physical Chemistry B, 106 (7). pp. 1714-1721. ISSN 1520-6106. doi:10.1021/jp0128933.

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The Karstedt-catalyzed hydrosilylation reaction used in curing of silicone release coatings was investigated using first-principle quantum mechanical techniques (density functional theory) as well as semiempirical methods to estimate solubility parameters. The results we obtain for the catalytic cycle indicate, in agreement with experimental results, that hydrosilylation occurs easily at room temperature. The detailed mechanism we suggest contains the key features of the models previously proposed in the literature by Lewis and Chalk−Harrod and adds quantitative estimates of reaction energies and barriers. On the basis of the energy profile for the catalytic cycle in the presence of inhibitor molecules and on solubility parameters for the species involved in the reaction, we conclude that the role of the inhibitors we considered is to phase-separate the catalyst from the substrate. The reaction is thus quenched by introducing a microscopic second phase that interferes with the homogeneous reaction.

Item Type:Article
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URLURL TypeDescription
Faglioni, Francesco0000-0002-3327-8848
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2002 American Chemical Society. Received: July 26, 2001; In Final Form: November 26, 2001. Publication Date (Web): January 30, 2002. This research is supported by grants from NPTO (DoE-FETC) and with funding from NSF (MRI and CHE 95-22179). The facilities of the MSC are also supported by grants from DoE ASCI ASAP, ARO-MURI, BP Amoco, Chevron Corp., NASA, Beckman Institute, Seiko-Epson, Exxon, Asahi Chemical, Avery-Dennison, Dow, and 3M. We thank Carl J. Bilgrien at Dow-Corning. We further thank Avery-Dennison for financial support.
Funding AgencyGrant Number
Department of Energy (DOE)UNSPECIFIED
NSFCHE 95-22179
Army Research Office (ARO)UNSPECIFIED
Chevron CorporationUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Dow Chemical CompanyUNSPECIFIED
Issue or Number:7
Record Number:CaltechAUTHORS:20170408-143126703
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Official Citation:Heterogeneous Inhibition of Homogeneous Reactions:  Karstedt Catalyzed Hydrosilylation Francesco Faglioni, Mario Blanco, William A. Goddard, III, and Dennis Saunders The Journal of Physical Chemistry B 2002 106 (7), 1714-1721 DOI: 10.1021/jp0128933
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75958
Deposited By: 1Science Import
Deposited On:25 Apr 2017 21:11
Last Modified:15 Nov 2021 16:56

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