TY - JOUR

T1 - The halogen bond with isocyano carbon reduces isocyanide odor

AU - Mikherdov, Alexander S.

AU - Novikov, Alexander S.

AU - Boyarskiy, Vadim P.

AU - Kukushkin, Vadim Yu.

N1 - Publisher Copyright: © 2020, The Author(s).

PY - 2020/12/1

Y1 - 2020/12/1

N2 - Predominantly, carbon atoms of various species function as acceptors of noncovalent interactions when they are part of a π-system. Here, we report on the discovery of a halogen bond involving the isocyano carbon lone pair. The co-crystallization or mechanochemical liquid-assisted grinding of model mesityl isocyanide with four iodoperfluorobenezenes leads to a series of halogen-bonded adducts with isocyanides. The obtained adducts were characterized by single-crystal and powder X-ray diffraction, solid-state IR and 13C NMR spectroscopies, and also by thermogravimetric analysis. The formation of the halogen bond with the isocyano group leads to a strong reduction of the isocyanide odor (3- to 46-fold gas phase concentration decrease). This manipulation makes isocyanides more suitable for laboratory storage and usage while preserving their reactivity, which is found to be similar between the adducts and the parent isocyanide in some common transformations, such as ligation to metal centers and the multi-component Ugi reaction.

AB - Predominantly, carbon atoms of various species function as acceptors of noncovalent interactions when they are part of a π-system. Here, we report on the discovery of a halogen bond involving the isocyano carbon lone pair. The co-crystallization or mechanochemical liquid-assisted grinding of model mesityl isocyanide with four iodoperfluorobenezenes leads to a series of halogen-bonded adducts with isocyanides. The obtained adducts were characterized by single-crystal and powder X-ray diffraction, solid-state IR and 13C NMR spectroscopies, and also by thermogravimetric analysis. The formation of the halogen bond with the isocyano group leads to a strong reduction of the isocyanide odor (3- to 46-fold gas phase concentration decrease). This manipulation makes isocyanides more suitable for laboratory storage and usage while preserving their reactivity, which is found to be similar between the adducts and the parent isocyanide in some common transformations, such as ligation to metal centers and the multi-component Ugi reaction.

KW - Crystal engineering

KW - Halogen bonding

KW - Synthetic chemistry methodology

KW - EXPONENT BASIS-SETS

KW - THERMOCHEMISTRY

KW - COMPLEXES

KW - NONCOVALENT INTERACTIONS

KW - ISONITRILES

KW - CHALCOGEN

KW - SOLID-STATE

KW - DENSITY FUNCTIONALS

KW - COMPACT EFFECTIVE POTENTIALS

KW - EFFICIENT

UR - http://www.scopus.com/inward/record.url?scp=85086325781&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/9f1b785c-7212-392a-be57-68df5b88f5b3/

U2 - 10.1038/s41467-020-16748-x

DO - 10.1038/s41467-020-16748-x

M3 - Article

C2 - 32523100

VL - 11

JO - Nature Communications

JF - Nature Communications

SN - 2041-1723

IS - 1

M1 - 2921

ER -