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Theoretical, Solid‐State, and Solution Quantification of the Hydrogen Bond‐Enhanced Halogen Bond
Author(s) -
Decato Daniel A.,
Riel Asia Marie S.,
May James H.,
Bryantsev Vyacheslav S.,
Berryman Orion B.
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202012262
Subject(s) - halogen bond , hydrogen bond , halogen , chemistry , halide , crystallography , low barrier hydrogen bond , non covalent interactions , single bond , sextuple bond , bond order , bond length , computational chemistry , crystal structure , inorganic chemistry , molecule , organic chemistry , group (periodic table) , alkyl
Proximal noncovalent forces are commonplace in natural systems and understanding the consequences of their juxtaposition is critical. This paper experimentally quantifies for the first time a Hydrogen Bond‐Enhanced Halogen Bond (HBeXB) without the complexities of protein structure or preorganization. An HBeXB is a halogen bond that has been strengthened when the halogen donor simultaneously accepts a hydrogen bond. Our theoretical studies suggest that electron‐rich halogen bond donors are strengthened most by an adjacent hydrogen bond. Furthermore, stronger hydrogen bond donors enhance the halogen bond the most. X‐ray crystal structures of halide complexes (X − =Br − , I − ) reveal that HBeXBs produce shorter halogen bonds than non‐hydrogen bond analogues. 19 F NMR titrations with chloride highlight that the HBeXB analogue exhibits stronger binding. Together, these results form the foundation for future studies concerning hydrogen bonds and halogen bonds in close proximity.