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Issue 14, 2013
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A mechanistic analysis of the tetrasilyl-substituted trimetallaallenes, >E[double bond, length as m-dash]E[double bond, length as m-dash]E< (E = C, Si, Ge, Sn, and Pb)

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Abstract

The potential energy surfaces for the chemical reactions of tetrasilyl-substituted trimetallaallenes containing two cumulative E[double bond, length as m-dash]E double bonds, where E = C, Si, Ge, Sn, and Pb, are studied using density functional theory (B3LYP/LANL2DZ). Two types of chemical reactions, methanol addition and intramolecular 1,2-silyl migration, are used to study the reactivity of these allene analogues. The theoretical investigations suggest that the relative reactivity increases in the order: >C[double bond, length as m-dash]C[double bond, length as m-dash]C< ≪ >Si[double bond, length as m-dash]Si[double bond, length as m-dash]Si< < >Ge[double bond, length as m-dash]Ge[double bond, length as m-dash]Ge< < >Sn[double bond, length as m-dash]Sn[double bond, length as m-dash]Sn< < >Pb[double bond, length as m-dash]Pb[double bond, length as m-dash]Pb<. That is, the heavier the atomic weight of the group 14 atom (E), the more reactive is the >E[double bond, length as m-dash]E[double bond, length as m-dash]E< towards chemical reactions. Electronic (due to the group 14 element E) and steric (due to four bulky t-Bu2MeSi groups) factors play a key role in determining both the geometrical structures and the reactivity of the tetrasilyl-substituted trimetallaallenes, from both kinetic and thermodynamic viewpoints. A configuration mixing model, based on the work of Pross and Shaik, is used to rationalize the computational results. The results obtained allow a number of predictions, such as the reactivities and the reaction mechanisms of heavy allenes, to be made.

Graphical abstract: A mechanistic analysis of the tetrasilyl-substituted trimetallaallenes, >E [[double bond, length as m-dash]] E [[double bond, length as m-dash]] E< (E = C, Si, Ge, Sn, and Pb)

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Publication details

The article was received on 05 Dec 2012, accepted on 04 Jan 2013 and first published on 07 Jan 2013


Article type: Paper
DOI: 10.1039/C2DT32917D
Dalton Trans., 2013,42, 4873-4884

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    A mechanistic analysis of the tetrasilyl-substituted trimetallaallenes, >E[double bond, length as m-dash]E[double bond, length as m-dash]E< (E = C, Si, Ge, Sn, and Pb)

    M. Su and L. Liu, Dalton Trans., 2013, 42, 4873
    DOI: 10.1039/C2DT32917D

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