Olefin isomerization and hydrosilylation catalysis by lewis acidic organofluorophosphonium salts

Manuel Pérez; Lindsay J. Hounjet; Christopher B. Caputo; Roman Dobrovetsky; Douglas W. Stephan

doi:10.1021/ja410379x

Olefin isomerization and hydrosilylation catalysis by lewis acidic organofluorophosphonium salts

Manuel Pérez, Lindsay J. Hounjet, Christopher B. Caputo, Roman Dobrovetsky, Douglas W. Stephan

Research output: Contribution to journal › Article › peer-review

Abstract

Organofluorophosphonium salts of the formula [(C₆F ₅)_3-xPh_xPF][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.

Original language	English
Pages (from-to)	18308-18310
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	135
Issue number	49
DOIs	https://doi.org/10.1021/ja410379x
State	Published - 11 Dec 2013
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Olefin isomerization and hydrosilylation catalysis by lewis acidic organofluorophosphonium salts",

abstract = "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.",

author = "Manuel P{\'e}rez and Hounjet, \{Lindsay J.\} and Caputo, \{Christopher B.\} and Roman Dobrovetsky and Stephan, \{Douglas W.\}",

year = "2013",

month = dec,

day = "11",

doi = "10.1021/ja410379x",

language = "الإنجليزيّة",

volume = "135",

pages = "18308--18310",

journal = "Journal of the American Chemical Society",

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publisher = "American Chemical Society",

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T1 - Olefin isomerization and hydrosilylation catalysis by lewis acidic organofluorophosphonium salts

AU - Pérez, Manuel

AU - Hounjet, Lindsay J.

AU - Caputo, Christopher B.

AU - Dobrovetsky, Roman

AU - Stephan, Douglas W.

PY - 2013/12/11

Y1 - 2013/12/11

N2 - 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.

AB - 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.

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U2 - 10.1021/ja410379x

DO - 10.1021/ja410379x

M3 - مقالة

SN - 0002-7863

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 49

ER -

Olefin isomerization and hydrosilylation catalysis by lewis acidic organofluorophosphonium salts

Abstract

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