Issue 24, 2019

Theoretical investigations of the reactivity of neutral molecules that feature an M[double bond, length as m-dash]M (M = B, Al, Ga, In, and Tl) double bond

Abstract

The geometry, the electronic structure and the reactivity of compounds that feature a central M[double bond, length as m-dash]M (M = group 13 element) double bond with two sterically bulky ligands (L1 = tBu2MeSi and L2 = NHCiPr), L1L2M[double bond, length as m-dash]ML1L2 (Rea-MM) are studied at the B3LYP-D3(BJ)/def2-SVP level of theory. The computational results show that the presence of a lighter group 13 M element (such as B, Al, and Ga) in Rea-MM results in a significant E[double bond, length as m-dash]E double bond character and a planar structure. However, Rea-InIn and Rea-TlTl adopt a trans-bent structure, which weakens the M[double bond, length as m-dash]M double bond. The ETS-NOCV (extended transition state-natural orbitals for chemical valence) method is used to determine the key factors that affect the reactivity of Rea-MM for its [2+2] cycloaddition reaction with ethylene. The ETS-NOCV analysis shows that only Rea-BB is inert in this cycloaddition reaction because it has large destabilizing interactions (ΔEPauli and ΔEdist) that result in a high activation barrier. This occurs because of the small radius of the B atom in the group 13 elements, which results in severe steric congestion between Rea-BB and ethylene. The present theoretical conclusions suggest that the formation of the double-bonded neutral L1L2M[double bond, length as m-dash]ML1L2 (in particular for M = Ga and In) compound should be undoubtedly one of the intriguing research targets.

Graphical abstract: Theoretical investigations of the reactivity of neutral molecules that feature an M [[double bond, length as m-dash]] M (M = B, Al, Ga, In, and Tl) double bond

Supplementary files

Article information

Article type
Paper
Submitted
12 Mar 2019
Accepted
14 May 2019
First published
14 May 2019

New J. Chem., 2019,43, 9364-9375

Theoretical investigations of the reactivity of neutral molecules that feature an M[double bond, length as m-dash]M (M = B, Al, Ga, In, and Tl) double bond

M. Yang and M. Su, New J. Chem., 2019, 43, 9364 DOI: 10.1039/C9NJ01294J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements