Mechanistic investigation of zinc-promoted silylation of phenylacetylene and chlorosilane: a combined experimental and computational study

Literature Information

Publication Date 2020-09-18
DOI 10.1039/D0CP04127K
Impact Factor 3.676
Authors

Pan Huang, Zhen Liu, Yunqi Shao, Shifeng Deng, Boping Liu


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Abstract

The zinc-promoted silylation method is of great importance to synthesize high-performance silicon-containing arylacetylene (PSA) resins in the industry. However, it is difficult to eliminate the accompanied by-product of terminal alkenes due to the lack of mechanistic understanding of the silylation. The initiation of zinc-promoted silylation is facilitated by the interaction between zinc and phenylacetylene. Our DFT calculations indicated that the intermolecular hydrogen transfer of phenylacetylene follows an ionic pathway, which generates a phenylacetylene anion and the corresponding alkene moieties on the zinc surface. The styrene by-product is observed in this stage, with its alkene moieties desorbing as radicals into the solvent under the high reaction temperature. Three possible intermediates of surface phenylacetylene anions were proposed including PhCC–Zn, PhCCZnCl, and (PhCC)2Zn. These carbanion–zinc intermediates undergo an SN2 reaction with Me3SiCl to afford the alkynylsilane on the zinc surface, which is calculated to be the rate-determining step for the zinc-promoted silylation reaction.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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