A computational study on the identity of the active catalyst structure for Ru(II) carboxylate assisted C–H activation in acetonitrile

Claire McMullin, Nasir Rajabi, James Hammerton

Research output: Contribution to journalArticle

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+6)”, [(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.
Original languageEnglish
Pages (from-to)6678-6686
Number of pages9
JournalOrganic & Biomolecular Chemistry
Volume17
Issue number27
DOIs
Publication statusPublished - 25 Jun 2019

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

@article{6d55ccc0a95746e788d50ed1bb2af3ad,
title = "A computational study on the identity of the active catalyst structure for Ru(II) carboxylate assisted C–H activation in acetonitrile",
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.",
author = "Claire McMullin and Nasir Rajabi and James Hammerton",
year = "2019",
month = "6",
day = "25",
doi = "10.1039/c9ob01092k",
language = "English",
volume = "17",
pages = "6678--6686",
journal = "Organic & Biomolecular Chemistry",
number = "27",

}

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

AU - Rajabi, Nasir

AU - Hammerton, James

PY - 2019/6/25

Y1 - 2019/6/25

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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85068803547&partnerID=8YFLogxK

U2 - 10.1039/c9ob01092k

DO - 10.1039/c9ob01092k

M3 - Article

VL - 17

SP - 6678

EP - 6686

JO - Organic & Biomolecular Chemistry

JF - Organic & Biomolecular Chemistry

IS - 27

ER -