DFT Study of C-C and C-N Coupling on a Quintuple-Bonded Cr2 Template: MECP (Minimum Energy Crossing Point) Barriers Control Product Distribution

Ghorai, S and Jemmis, ED (2020) DFT Study of C-C and C-N Coupling on a Quintuple-Bonded Cr2 Template: MECP (Minimum Energy Crossing Point) Barriers Control Product Distribution. In: Organometallics, 39 (10). pp. 1700-1709.

	PDF ORG_39_10_1700-1709_2020.pdf - Published Version Restricted to Registered users only Download (5MB) | Request a copy
	Archive (ZIP) 4971926.zip - Published Supplemental Material Download (2MB)
Preview	PDF om9b00841_si_001.pdf - Published Supplemental Material Download (2MB) | Preview

Abstract

A detailed DFT study involving 50 intermediates, 26 transition states, a range of spin multiplicities and 3 MECPs explains the products (and their distribution) of the reaction of cyclohexyl isocyanide with the Cr-Cr quintuple-bonded complex LCr2 (L = N,N�-bis(2,6-diisopropylphenyl-1,4-diazadiene). Using methyl isocyanide as the prototypical isocyanide and LCr2 (L = N,N�-bis(2,6-dimethyl-1,4-diazadiene) as the quintuple-bonded system, mechanistic pathways for the formation of diamagnetic LCr(MeNC)4 (2b) and paramagnetic L2Cr2C4(NMe)4](MeNC)2] (3b) and L2Cr2C6(NMe)6]] (4b) with an excess of isocyanide and of a paramagnetic product of C-H activation (5b) with 4 equiv of isocyanide are obtained. The ground-state electronic configurations of different products are discussed using an electron-counting scheme. Barriers for minimum energy crossing points (MECPs) and for different transition states control the experimental product distributions. © 2020 American Chemical Society.

Item Type:	Journal Article
Publication:	Organometallics
Publisher:	American Chemical Society
Additional Information:	Copy right for this article belongs to American Chemical Society
Keywords:	Diimides,Inorganic carbon compounds,Basis sets,Quantum mechanics,Ligands
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	22 Dec 2020 11:23
Last Modified:	22 Dec 2020 11:23
URI:	http://eprints.iisc.ac.in/id/eprint/65880

Actions (login required)

View Item