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.
Highlights
Carbon atoms of various species function as acceptors of noncovalent interactions when they are part of a π-system
The solid-state interaction involving the carbon lone pair and halogen atom has been previously observed in only one case, namely in the adduct (IAd)IPFB formed upon the interplay of iodopentafluorobenzene (IPFB) and N-heterocyclic carbene (IAd)[16]
We report our discovery of a halogen bond between the lone pair of the isocyanide carbon atom and σ-holes of iodine centers of iodo-substituted perfluoroarenes
Summary
Carbon atoms of various species function as acceptors of noncovalent interactions when they are part of a π-system. The solid-state interaction involving the carbon lone pair (lp) and halogen atom has been previously observed in only one case, namely in the adduct (IAd)IPFB formed upon the interplay of iodopentafluorobenzene (IPFB) and N-heterocyclic carbene (IAd)[16].
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