Alkynophilicity of Group 13 MX3 Salts: A Theoretical Study

Alkynophilicity of Group 13 MX3 Salts: A Theoretical Study

The concept of alkynophilicity is revisited with group 13 MX3 metal salts (M = In, Ga, Al, B; X = Cl, OTf) using M06-2X/6-31+G­(d,p) calculations. This study aims at answering why some of these salts show reactivity toward enynes that is similar to that observed with late-transition-metal complexes,...

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Veröffentlicht in:Inorganic chemistry 2021-04, Vol.60 (8), p.5507-5522
Hauptverfasser: Yang, Shengwen, Alix, Aurélien, Bour, Christophe, Gandon, Vincent
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creator Yang, Shengwen
Alix, Aurélien
Bour, Christophe
Gandon, Vincent
description The concept of alkynophilicity is revisited with group 13 MX3 metal salts (M = In, Ga, Al, B; X = Cl, OTf) using M06-2X/6-31+G­(d,p) calculations. This study aims at answering why some of these salts show reactivity toward enynes that is similar to that observed with late-transition-metal complexes, notably Au­(I) species, and why some of them are inactive. For this purpose, the mechanism of the skeletal reorganization of 1,6-enynes into 1-vinylcyclopentenes has been computed, including monomeric (“standard”) and dimeric (superelectrophilic) activation. Those results are confronted with deactivation pathways based on the dissociation of the M–X bond. The role of the X ligand in the stabilization of the intermediate nonclassical carbocation is revealed, and the whole features required to make a good π-Lewis acid are discussed.
doi_str_mv 10.1021/acs.inorgchem.0c03302
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title Alkynophilicity of Group 13 MX3 Salts: A Theoretical Study
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