Comparison of RNC Coupling and CO Coupling Mediated by Cr-Cr Quintuple Bond and B-B Multiple Bonds: Main Group Metallomimetics

Ghorai, S and Meena, R and Joseph, AP and Jemmis, ED (2021) Comparison of RNC Coupling and CO Coupling Mediated by Cr-Cr Quintuple Bond and B-B Multiple Bonds: Main Group Metallomimetics. In: Journal of Physical Chemistry A .

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Abstract

A theoretical analysis of reductive coupling of isocyanide and CO mediated by a Cr-Cr quintuple bonded complex and B-B multiple bonded complexes shows how the difference in donor-acceptor capability of isocyanide and CO ligands controls the product distributions. In the case of CO, the Cr-Cr quintuple bonded complex is unable to show C-C coupling due to the high �-back bonding possibility of CO and the reaction follows the singlet potential energy surface throughout, whereas, in the case of isocyanide, less �-back bonding possibility allows the reactions to undergo a spin transition and gives a series of products with different spin multiplicities. Similarly, reactions of B-B multiple bonded complexes with CO and isocyanides are also controlled by donor-acceptor capabilities of ligands, and the C-C coupling takes place by changing the oxidation state of the boron centers from +I to +II, in contrast to the classical main group mediated reactions where stable oxidation states are always preserved. This part of the main group chemistry which is dominated by donor-acceptor bonding interaction is more likely to follow transition metal behavior. © 2021 American Chemical Society.

Item Type:	Journal Article
Publication:	Journal of Physical Chemistry A
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society
Keywords:	Binary alloys; Chemical bonds; Cyanides; Ligands; Potential energy; Quantum chemistry; Transition metals, Bonding interactions; Main group chemistry; Mediated reactions; Oxidation state; Product distributions; Reductive couplings; Spin multiplicity; Spin transition, Chromium compounds
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	03 Dec 2021 08:16
Last Modified:	03 Dec 2021 08:16
URI:	http://eprints.iisc.ac.in/id/eprint/70174

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