The halogen bond with isocyano carbon reduces isocyanide odor.

Nature Communications
Alexander S MikherdovVadim Yu Kukushkin

Abstract

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.

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Citations

Oct 4, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Steve Scheiner
Oct 9, 2020·Chemical Society Reviews·Matthias KnornOliver Reiser
Oct 24, 2020·Chemistry : a European Journal·Jenni FroschMatthias Tamm
Feb 11, 2021·Journal of Computational Chemistry·Fernando Jiménez-GrávalosAlexander S Novikov
Mar 9, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Firas F AwwadiBrendan Twamley
Jul 3, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Mikhail A VershininSergey A Adonin
Jul 2, 2021·Chemical Reviews·Alberto MassarottiGian Cesare Tron
Oct 9, 2021·Chemistry : a European Journal·Daniil M IvanovAntonio Frontera

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Methods Mentioned

BETA
X-ray
NMR
co-crystallization

Software Mentioned

Multiwfn
QTAIM
Gaussian
SHELX
ConQuest
Chemcraft
OLEX2

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