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Gas-phase intramolecular anion rearrangements of some trimethylsilyl-containing systems revisited. A theoretical approach
Journal article   Peer reviewed

Gas-phase intramolecular anion rearrangements of some trimethylsilyl-containing systems revisited. A theoretical approach

Tianfang Wang and J H Bowie
Rapid Communications in Mass Spectrometry, Vol.24(1), pp.57-62
2010
DOI: https://doi.org/10.1002/rcm.4363
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https://doi.org/10.1002/rcm.4363View
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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: CH2 = C(O-)Si(CH3)3 → (CH3)3SiO- + CH2H, and (CH3)3SiCH = CHO- → (CH3)3SiO- = C2H2.The ΔG (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: (CH3O)C(CH2)Si(CH3)2CH → (CH3)2(C2H5)Si- + CH2CO, a process involving an Sni reaction between -CH and CH3O- followed by silicon-carbon bond cleavage. The reaction is favourable [ΔG(reaction) = -39 kJ mol-1] with the barrier for the Sni process being 175 kJ mol-1. The previous experimental and the current theoretical data are complementary and in agreement.

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