Display options
Cite
Bottoni A, Higueruelo AP, Miscione GP. A DFT computational study of the bis-silylation reaction of acetylene catalyzed by palladium complexes. J Am Chem Soc. 2002;124(19):5506-13doi: 10.1021/ja0118892.
Bottoni, A., Higueruelo, A. P., & Miscione, G. P. (2002). A DFT computational study of the bis-silylation reaction of acetylene catalyzed by palladium complexes. Journal of the American Chemical Society, 124(19), 5506-13. https://doi.org/10.1021/ja0118892
Bottoni, Andrea, et al. "A DFT computational study of the bis-silylation reaction of acetylene catalyzed by palladium complexes." Journal of the American Chemical Society vol. 124,19 (2002): 5506-13. doi: https://doi.org/10.1021/ja0118892
Bottoni A, Higueruelo AP, Miscione GP. A DFT computational study of the bis-silylation reaction of acetylene catalyzed by palladium complexes. J Am Chem Soc. 2002 May 15;124(19):5506-13. doi: 10.1021/ja0118892. PMID: 11996593.
Copy Download .nbib Format: NLM
Share it on

J Am Chem Soc. 2002 May 15;124(19):5506-13. doi: 10.1021/ja0118892.

A DFT computational study of the bis-silylation reaction of acetylene catalyzed by palladium complexes.

Journal of the American Chemical Society

Andrea Bottoni, Alicia Perez Higueruelo, Gian Pietro Miscione

Affiliations

  1. Dipartimento di Chimica "G.Ciamician", Universita' di Bologna, via Selmi 2, 40126 Bologna, Italy. [email protected]

PMID: 11996593 DOI: 10.1021/ja0118892

Abstract

In this paper we have investigated at the DFT(B3LYP) level the catalytic cycle for the bis-silylation reaction of alkynes promoted by palladium complexes. A model-system formed by an acetylene molecule, a disilane molecule, and the Pd(PH(3))(2) complex has been used. The most relevant features of this catalytic cycle can be summarized as follows: (i) The first step of the cycle is an oxidative addition involving H(3)Si-SiH(3) and Pd(PH(3))(2). It occurs easily and leads to the cis (SiH(3))(2)Pd(PH(3))(2) complex that is 5.39 kcal mol(-1) lower in energy than reactants. (ii) The transfer of the two silyl groups to the C-C triple bond does not occur in a concerted way, but involves many steps. (iii) The cis (SiH(3))(2)Pd(PH(3))(2) complex, obtained from the oxidative addition, is involved in the formation of the first C-Si bond (activation barrier of 18.34 kcal mol(-1)). The two intermediates that form in this step cannot lead directly to the formation of the final bis(silyl)ethene product. However, they can isomerize rather easily (the two possible isomerizations have a barrier of 16.79 and 7.17 kcal mol(-1)) to new more stable species. In both these new intermediates the second silyl group is adjacent to the acetylene moiety and the formation of the second C-Si bond can occur rapidly leading to the (Z)-bis(silyl)ethene, as experimentally observed. (iv) The whole catalytic process is exothermic by 41.54 kcal mol(-1), in quite good agreement with the experimental estimate of this quantity (about 40 kcal mol(-1)).

Publication Types