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https://hdl.handle.net/2440/57746
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Type: | Journal article |
Title: | Gas-phase intramolecular anion rearrangements of some trimethylsilyl-containing systems revisited. A theoretical approach |
Author: | Wang, T. Bowie, J. |
Citation: | Rapid Communications in Mass Spectrometry, 2010; 24(1):57-62 |
Publisher: | John Wiley & Sons Ltd |
Issue Date: | 2010 |
ISSN: | 0951-4198 1097-0231 |
Statement of Responsibility: | Tianfang Wang and John H. Bowie |
Abstract: | Ab initio calculations at the CCSD(T)/6-311++G(2d,p)//B3LYP/6-311++G(d,p) level of theory have been carried out for three prototypical rearrangement processes of organosilicon anion systems. The first two are reactions of enolate ions which involve oxygen-silicon bond formation via three- and four-membered states, respectively. The overall reactions are: CH(2) = C(O(-))Si(CH(3))(3) --> (CH(3))(3)SiO(-) + CH(2)C, and (CH(3))(3)SiCH = CHO(-) --> (CH(3))(3)SiO(-) + C(2)H(2). The DeltaG (reaction) values for the two processes are +175 and +51 kJ mol(-1), with maximum barriers (to the highest transition state) of +55 and +159 kJ mol(-1), respectively. The third studied process is the following: (CH(3)O)C(=CH(2))Si(CH(3))(2)CH(2)(-) --> (CH(3))(2)(C(2)H(5))Si(-) + CH(2)CO, a process involving an S(N)i reaction between -CH(2)(-) and CH(3)O- followed by silicon-carbon bond cleavage. The reaction is favourable [DeltaG(reaction) = -39 kJ mol(-1)] with the barrier for the S(N)i process being 175 kJ mol(-1). The previous experimental and the current theoretical data are complementary and in agreement. |
Description: | Published Online: 4 Dec 2009 Copyright © 2009 John Wiley & Sons, Ltd. |
DOI: | 10.1002/rcm.4363 |
Grant ID: | ARC |
Published version: | http://dx.doi.org/10.1002/rcm.4363 |
Appears in Collections: | Aurora harvest Chemistry publications |
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