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The effect of coordination of alkanes, Xe and CO2 (?1-OCO) on changes in spin state and reactivity in organometallic chemistry: a combined experimental and theoretical study of the photochemistry of CpMn(CO)3

Wu, Xue; Liu, Zhen; Murphy, Thomas S.; Sun, Xue Z.; Hanson-Heine, Magnus W. D.; Towrie, Michael; Harvey, Jeremy N.; George, Michael W.

The effect of coordination of alkanes, Xe and CO2 (?1-OCO) on changes in spin state and reactivity in organometallic chemistry: a combined experimental and theoretical study of the photochemistry of CpMn(CO)3 Thumbnail


Authors

Xue Wu

Zhen Liu

Thomas S. Murphy

Magnus W. D. Hanson-Heine

Michael Towrie

Jeremy N. Harvey



Abstract

A combined experimental and theoretical study is presented of several ligand addition reactions of the triplet fragment 3CpMn(CO)2 formed upon photolysis of CpMn(CO)3. Experimental data are provided for reactions in n-heptane and perfluoromethylcyclohexane (PFMCH), as well as in PFMCH doped with C2H6, Xe and CO2. In PFMCH we find that the conversion of 3CpMn(CO)2 to 1CpMn(CO)2(PFMCH) is much slower (τ = 18 (±3) ns) than the corresponding reactions in conventional alkanes (τ = 111 (±10) ps). We measure the effect of the coordination ability by doping PFMCH with alkane, Xe and CO2; these doped ligands form the corresponding singlet adducts with significantly variable formation rates. The reactivity as measured by the addition timescale follows the order 1CpMn(CO)2(C5H10) (τ = 270 (±10) ps) > 1CpMn(CO)2Xe (τ = 3.9 (±0.4) ns) ∼ 1CpMn(CO)2(CO2) (τ = 4.7 (±0.5) ns) > 1CpMn(CO)2(C7F14) (τ = 18 (±3) ns). Electronic structure theory calculations of the singlet and triplet potential energy surfaces and of their intersections, together with non-adiabatic statistical rate theory, reproduce the observed rates semi-quantitatively. It is shown that triplet adducts of the ligand and 3CpMn(CO)2 play a role in the kinetics, and account for the variable timescales observed experimentally.

Citation

Wu, X., Liu, Z., Murphy, T. S., Sun, X. Z., Hanson-Heine, M. W. D., Towrie, M., …George, M. W. (2019). The effect of coordination of alkanes, Xe and CO2 (η1-OCO) on changes in spin state and reactivity in organometallic chemistry: a combined experimental and theoretical study of the photochemistry of CpMn(CO)3. Faraday Discussions, 220, 86-104. https://doi.org/10.1039/c9fd00067d

Journal Article Type Article
Acceptance Date Jul 4, 2019
Online Publication Date Oct 14, 2019
Publication Date Dec 2, 2019
Deposit Date Oct 28, 2019
Publicly Available Date Mar 29, 2024
Journal Faraday Discussions
Print ISSN 1359-6640
Electronic ISSN 1364-5498
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 220
Pages 86-104
DOI https://doi.org/10.1039/c9fd00067d
Public URL https://nottingham-repository.worktribe.com/output/2977300
Publisher URL https://pubs.rsc.org/en/content/articlelanding/2019/FD/C9FD00067D#!divAbstract
Additional Information : This document is Similarity Check deposited; : Supplementary Information; : Zhen Liu (ORCID); : Zhen Liu (ResearcherID); : Thomas S. Murphy (ORCID); : Jeremy N. Harvey (ORCID); : Jeremy N. Harvey (ResearcherID); : Michael W. George (ORCID); : Single-blind; : Received 13 May 2019; Accepted 4 July 2019; Advance Article published 14 October 2019

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