(Isocyano group)⋯lone pair interactions involving coordinated isocyanides: experimental, theoretical and CSD studies

Mikherdov, Alexander S.; Katkova, Svetlana A.; Novikov, Alexander S.; Efremova, Mariia M.; Reutskaya, Elena; Kinzhalov, Mikhail A.

doi:10.1039/c9ce01741k

Cited by 25 publications

(18 citation statements)

References 52 publications

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“…In the second contact, ∠(C-I•••C) 79.50 (14)°and ∠(I•••C ≡ N) 94.9 (3)°are close to 90°and, accordingly 8 , this interaction cannot be recognized as XB. Previously, we reported a similar interaction pattern for (isocyano group)•••lp 23,24 and (isocyano group)•••πsystem 29 contacts observed for metal-bound CNR; in these systems the isocyano fragment acted as a π-hole donor. We assume that in the case of (CNMes)•IPFB, the longer I•••C contact could also have a contribution of π-hole•••lp interaction involving the π-system of the isocyanide group and lp of the iodine atom.…”

Section: Solution and Mechanochemical Routes To Isocyanide Adductssupporting

confidence: 73%

“…Taking into account our general interest in the isocyanide chemistry (for our relevant review see ref. 21 ) and, in particular, isocyanide involving crystal engineering [22][23][24][25][26] , we focused our efforts on isocyanide species (CNR) featuring potential lp at the C atom. As a model XB acceptor for this study we addressed the isocyanide CNMes because of its broad usage, commercial availability, and excellent solubility in nonpolar solvents.…”

Section: Solution and Mechanochemical Routes To Isocyanide Adductsmentioning

confidence: 99%

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The halogen bond with isocyano carbon reduces isocyanide odor

et al. 2020

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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 13 C 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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Section: Solution and Mechanochemical Routes To Isocyanide Adductssupporting

confidence: 73%

Section: Solution and Mechanochemical Routes To Isocyanide Adductsmentioning

confidence: 99%

The halogen bond with isocyano carbon reduces isocyanide odor

et al. 2020

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“…It has been shown recently that, after coordination with a metal, both the nitrogen and the carbon atom of isocyanides can act as π-hole acceptors to the electron lone pairs of various kinds of atoms. , In the same article, the authors propose that the interaction with the nitrogen atom of isocyanide is more electrostatic and longer, while the interaction with the carbon atom of isocyanide is predominantly a charge-transfer complex which requires shorter distance in order to favor the n-π* electron transition. This interesting interaction should not be missed in medicinal chemistry, whenever an isocyanide acts as coordinative group with a metal ion present in an active site (Figure ).…”

Section: Chemical Features Of the Isocyanide Groupmentioning

confidence: 99%

Medicinal Chemistry of Isocyanides

et al. 2021

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In eons of evolution, isocyanides carved out a niche in the ecological systems probably thanks to their metal coordinating properties. In 1859 the first isocyanide was synthesized by humans and in 1950 the first natural isocyanide was discovered. Now, at the beginning of XXI century, hundreds of isocyanides have been isolated both in prokaryotes and eukaryotes and thousands have been synthesized in the laboratory. For some of them their ecological role is known, and their potent biological activity as antibacterial, antifungal, antimalarial, antifouling, and antitumoral compounds has been described. Notwithstanding, the isocyanides have not gained a good reputation among medicinal chemists who have erroneously considered them either too reactive or metabolically unstable, and this has restricted their main use to technical applications as ligands in coordination chemistry. The aim of this review is therefore to show the richness in biological activity of the isocyanidecontaining molecules, to support the idea of using the isocyanide functional group as an unconventional pharmacophore especially useful as a metal coordinating warhead. The unhidden hope is to convince the skeptical medicinal chemists of the isocyanide potential in many areas of drug discovery and considering them in the design of future drugs.

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“…72 We have also previous experience on the successful application of such basis sets in studies of NCIs 73,74 and, in particular, in chemical systems containing heavy atoms (noble metals, iodine). 75,76 In addition, the RESC scalar relativistic approach, 77 as implemented in G09, was employed for all compounds that include iodine.…”

Section: Computational Detailsmentioning

confidence: 99%

Challenging the electrostatic σ‐hole picture of halogen bonding using minimal models and the interacting quantum atoms approach

et al. 2021

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Among the different noncovalent interactions, halogen bonds have captured wide attention in the last years. Their stability has been rationalized in electrostatic terms by appealing to the σ-hole concept, a charge-depleted region that is able to interact favorably with electron rich moieties. This interpretation has been questioned, and in this work a set of anionic halogen model systems are used to shed some light on this issue. We use the interacting quantum atoms method, which provides an orbital invariant energy decomposition in which pure electrostatic terms are well isolated, and we complement our insights with the analysis of electrostatic potentials (ESPs) as well as with traditional descriptors of charge accumulation like the Laplacian of the electron density. The total electrostatic interaction between the interacting species is surprisingly destabilizing in many of the systems examined, demonstrating that although σ-holes might be qualitatively helpful, much care has to be taken in ascribing the stability of these systems to electrostatics. It is clearly shown that electron delocalization is essential to understand the stability of the complexes. The evolution of atomic charges as the aggregates forms reveals a charge transfer picture in which the central, σ-hole bearing halogen acts as a mere spectator. These systems may then be not far from engaging in a classical 3c-4e interaction. Since the presence of a σ-hole as characterized by the ESP mapped on a suitable molecular envelope isosurface does not guarantee attractive electrostatic interactions, we encourage to employ a wider perspective that takes into account the full charge distribution.

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(Isocyano group)⋯lone pair interactions involving coordinated isocyanides: experimental, theoretical and CSD studies

Abstract: Both carbon and nitrogen centers in the coordinated isocyano group are capable of acting as a π-hole donor toward lone pairs.

Cited by 25 publications

References 52 publications

The halogen bond with isocyano carbon reduces isocyanide odor

The halogen bond with isocyano carbon reduces isocyanide odor

Medicinal Chemistry of Isocyanides

Challenging the electrostatic σ‐hole picture of halogen bonding using minimal models and the interacting quantum atoms approach

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