Sulfur dioxide insertion into aryl carbon-tin bonds: kinetics and mechanism

Fong C.W. and Kitching W. (1973) Sulfur dioxide insertion into aryl carbon-tin bonds: kinetics and mechanism. Journal of Organometallic Chemistry, 59 C: 213-223. doi:10.1016/S0022-328X(00)95037-X

Author Fong C.W.
Kitching W.
Title Sulfur dioxide insertion into aryl carbon-tin bonds: kinetics and mechanism
Journal name Journal of Organometallic Chemistry   Check publisher's open access policy
ISSN 0022-328X
Publication date 1973-10-01
Sub-type Article (original research)
DOI 10.1016/S0022-328X(00)95037-X
Volume 59
Issue C
Start page 213
End page 223
Total pages 11
Language eng
Subject 1303 Specialist Studies in Education
1501 Accounting, Auditing and Accountability
1604 Human Geography
1605 Policy and Administration
1606 Political Science
2501 Materials Science (miscellaneous)
2505 Materials Chemistry
Abstract A kinetic study of the insertion of sulfur dioxide into the aryl carbon-tin bond of a species of 3- and 4-substituted phenyltrimethyl stannanes in anhydrous methanol has been conducted. The reaction is cleanly second order in this solvent (first order in each of stannane and sulfur dioxide) and the second order rate constants show an excellent correlation with σ+, indicating an electrophilic insertion reaction. The low p value and a positive salt effect on the rate of insertion suggest a four centeredSEi transition state with some polar character. Sulfur dioxide is located in the electrophile reactivity series, CH3,COOH < SO2 < HCl < < I2 < < BR2 for this particular system. Whilst the insertion reaction in methanol is a second order process, the kinetic situation in benzene is more complex, with k2(obs) increasing with [SO2], and may be attributable to changes in the dielectric properties of the medium. The stereochemistry of insertion into a vinyltin bond is shown to involve essentially complete retention of configuration at carbon, as demanded by an SEi process.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Scopus Import
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