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A computational study on the identity of the active catalyst structure for Ru(ii) carboxylate assisted C-H activation in acetonitrile.
Org Biomol Chem 2019; 17(27):6678-6686OB

Abstract

Density Functional Theory (DFT) calculations using a consistent methodology accounting for solvation, dispersion and thermal effects have been used to study C-H activation of the simple directing group substrate 2-phenylpyridine (a-H). The computational model uses acetate (-OAc) and benzene to represent the carboxylate and arene co-ligands coordinated at a Ru organometallic complex. A variety of different mechanisms ranging from cationic to neutral, ion-paired, arene free, two substrates bound, and solvent (MeCN) coordinated have been explored. Computed results indicate that the cationic pathways from "B+", [(C6H6)Ru(OAc)(a-H)]+, and "D+ (η6)", [(η6-a-H)Ru(OAc)(a-H)]+, involve the lowest overall barriers to C-H activation. Consideration of solvent coordination leads to a complex variety of isomers and conformers. Here a neutral pathway with either one or two acetonitriles coordinated to the Ru centre give very low barriers to C-H activation.

Authors+Show Affiliations

Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK. c.mcmullin@bath.ac.uk.Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK. c.mcmullin@bath.ac.uk.Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK. c.mcmullin@bath.ac.uk.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31237301

Citation

McMullin, Claire L., et al. "A Computational Study On the Identity of the Active Catalyst Structure for Ru(ii) Carboxylate Assisted C-H Activation in Acetonitrile." Organic & Biomolecular Chemistry, vol. 17, no. 27, 2019, pp. 6678-6686.
McMullin CL, Rajabi NA, Hammerton JS. A computational study on the identity of the active catalyst structure for Ru(ii) carboxylate assisted C-H activation in acetonitrile. Org Biomol Chem. 2019;17(27):6678-6686.
McMullin, C. L., Rajabi, N. A., & Hammerton, J. S. (2019). A computational study on the identity of the active catalyst structure for Ru(ii) carboxylate assisted C-H activation in acetonitrile. Organic & Biomolecular Chemistry, 17(27), pp. 6678-6686. doi:10.1039/c9ob01092k.
McMullin CL, Rajabi NA, Hammerton JS. A Computational Study On the Identity of the Active Catalyst Structure for Ru(ii) Carboxylate Assisted C-H Activation in Acetonitrile. Org Biomol Chem. 2019 Jul 21;17(27):6678-6686. PubMed PMID: 31237301.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - A computational study on the identity of the active catalyst structure for Ru(ii) carboxylate assisted C-H activation in acetonitrile. AU - McMullin,Claire L, AU - Rajabi,Nasir A, AU - Hammerton,James S, Y1 - 2019/06/25/ PY - 2019/6/27/pubmed PY - 2019/6/27/medline PY - 2019/6/26/entrez SP - 6678 EP - 6686 JF - Organic & biomolecular chemistry JO - Org. Biomol. Chem. VL - 17 IS - 27 N2 - Density Functional Theory (DFT) calculations using a consistent methodology accounting for solvation, dispersion and thermal effects have been used to study C-H activation of the simple directing group substrate 2-phenylpyridine (a-H). The computational model uses acetate (-OAc) and benzene to represent the carboxylate and arene co-ligands coordinated at a Ru organometallic complex. A variety of different mechanisms ranging from cationic to neutral, ion-paired, arene free, two substrates bound, and solvent (MeCN) coordinated have been explored. Computed results indicate that the cationic pathways from "B+", [(C6H6)Ru(OAc)(a-H)]+, and "D+ (η6)", [(η6-a-H)Ru(OAc)(a-H)]+, involve the lowest overall barriers to C-H activation. Consideration of solvent coordination leads to a complex variety of isomers and conformers. Here a neutral pathway with either one or two acetonitriles coordinated to the Ru centre give very low barriers to C-H activation. SN - 1477-0539 UR - https://www.unboundmedicine.com/medline/citation/31237301/A_computational_study_on_the_identity_of_the_active_catalyst_structure_for_Ru(ii)_carboxylate_assisted_C-H_activation_in_acetonitrile L2 - https://doi.org/10.1039/c9ob01092k DB - PRIME DP - Unbound Medicine ER -