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

Autor:	Raghavendra Meena, Sagar Ghorai, Eluvathingal D. Jemmis, Anju P. Joseph
Rok vydání:	2021
Předmět:	chemistry.chemical_compound Crystallography Transition metal Oxidation state Chemistry Isocyanide Potential energy surface Spin transition Singlet state Physical and Theoretical Chemistry Quintuple bond Pi backbonding
Zdroj:	The Journal of Physical Chemistry A. 125:7207-7216
ISSN:	1520-5215 1089-5639
DOI:	10.1021/acs.jpca.1c05185
Popis:	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 π- back bonding possibility of CO and the reaction follows the singlet potential energy surface throughout, whereas, in the case of isocyanide, less π- 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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::d084d4a502e2f9ebce10f8bd72db9656 https://doi.org/10.1021/acs.jpca.1c05185 Zobrazit plný text záznamu