Azide-Alkyne Interactions: A Crucial Attractive Force for Their Preorganization for Topochemical Cycloaddition Reaction.
Chemistry
; 28(28): e202200820, 2022 May 16.
Article
em En
| MEDLINE
| ID: mdl-35302679
ABSTRACT
A new class of attractive intermolecular interaction between azide and ethynyl structural entities in a wide range of molecular crystals is reported. This interaction was systematically evaluated by using 11 geometrically different structural motifs that are preorganized to direct a solid-state topochemical azide-alkyne cycloaddition (TAAC) reaction. The supramolecular features of the azide-alkyne interaction were mapped by various crystallographic and quantum chemical approaches. Topological analysis shows the noticeable participation of electron density in the azideâ
â
â
alkyne interactions. Interestingly, reorientation of the atomic polarizabilities in vicinal azide and alkyne groups upon interaction in crystals favors soft orbital-guided TAAC reactions. Moreover, various solid-state and gas-phase energy decomposition methods of individual azideâ
â
â
alkyne interactions summarize that the strength (varies from -5.7 to -30.1â
kJ mol-1 ) is primarily guided by the dispersion forces with a influencing contribution from the electrostatics.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Azidas
/
Alcinos
Idioma:
En
Ano de publicação:
2022
Tipo de documento:
Article