{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T22:03:49Z","timestamp":1792015429711,"version":"4.4.0"},"reference-count":64,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2013,12,16]],"date-time":"2013-12-16T00:00:00Z","timestamp":1387152000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2014,1,20]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Kinetics of the reactions of benzhydrylium ions (Aryl<jats:sub>2<\/jats:sub>CH<jats:sup>+<\/jats:sup>) with the vinylsilanes H<jats:sub>2<\/jats:sub>C\uf8feC(CH<jats:sub>3<\/jats:sub>)(SiR<jats:sub>3<\/jats:sub>), H<jats:sub>2<\/jats:sub>C\uf8feC(Ph)(SiR<jats:sub>3<\/jats:sub>), and (<jats:italic>E<\/jats:italic>)\u2010PhCH\uf8feCHSiMe<jats:sub>3<\/jats:sub> have been measured photometrically in dichloromethane solution at 20\u2009\u00b0C. All reactions follow second\u2010order kinetics, and the second\u2010order rate constants correlate linearly with the electrophilicity parameters <jats:italic>E<\/jats:italic> of the benzhydrylium ions, thus allowing us to include vinylsilanes in the benzhydrylium\u2010based nucleophilicity scale. The vinylsilane H<jats:sub>2<\/jats:sub>C\uf8feC(CH<jats:sub>3<\/jats:sub>)(SiMe<jats:sub>3<\/jats:sub>), which is attacked by electrophiles at the CH<jats:sub>2<\/jats:sub> group, reacts one order of magnitude faster than propene, indicating that \u03b1\u2010silyl\u2010stabilization of the intermediate carbenium ion is significantly weaker than \u03b1\u2010methyl stabilization because H<jats:sub>2<\/jats:sub>C\uf8feC(CH<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub> is 10<jats:sup>3<\/jats:sup>\u2005times more reactive than propene. <jats:italic>trans<\/jats:italic>\u2010\u03b2\u2010(Trimethylsilyl)styrene, which is attacked by electrophiles at the silylated position, is even somewhat less reactive than styrene, showing that the hyperconjugative stabilization of the developing carbocation by the \u03b2\u2010silyl effect is not yet effective in the transition state. As a result, replacement of vinylic hydrogen atoms by SiMe<jats:sub>3<\/jats:sub> groups affect the nucleophilic reactivities of the corresponding C\uf8feC bonds only slightly, and vinylsilanes are significantly less nucleophilic than structurally related allylsilanes.<\/jats:p>","DOI":"10.1002\/chem.201303215","type":"journal-article","created":{"date-parts":[[2013,12,16]],"date-time":"2013-12-16T15:29:44Z","timestamp":1387207784000},"page":"1103-1110","source":"Crossref","is-referenced-by-count":26,"title":["Electrophilic Alkylations of Vinylsilanes: A Comparison of \u03b1\u2010 and \u03b2\u2010Silyl Effects"],"prefix":"10.1002","volume":"20","author":[{"given":"Hans A.","family":"Laub","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Herbert","family":"Mayr","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2013,12,16]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","volume-title":"Organosilicon Compounds","author":"Eaborn C.","year":"1960"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/cs9780700015"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1979-28829"},{"key":"e_1_2_6_5_2","volume-title":"Silicon in Organic Synthesis","author":"Colvin E. 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