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    An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)5MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory


    McMahon, Suzanne and Amirjalayer, Saeed and Buma, Wybren J. and Halpin, Yvonne and Long, Conor and Rooney, A. Denise and Woutersenc, Sander and Pryce, Mary T. (2015) An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)5MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory. Dalton Transactions, 44 (35). pp. 15424-15434. ISSN 1477-9226

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    Abstract

    The photophysics and photochemistry of [(CO)5MC(OMe)Me] (M = Cr or W) were investigated using picosecond time-resolved infrared spectroscopy (M = Cr or W), low-temperature matrix isolation techniques (M = Cr), and time-dependent density functional calculations (M = Cr or W). These studies provide unambiguous evidence for the photochemical formation of a long-lived, 18-electron metallaketene species capable of acting as a synthetically useful intermediate. For the Cr complex, an intermediate metallacyclopropanone singlet excited state was detected on the reaction path to the metallaketene species. This metallacyclopropanone excited state species has a lifetime of less than 100 ps and a characteristic bridging carbonyl band at 1770 cm−1. The tungsten ketene species was also detected but in contrast to the chromium system, this forms directly from a low-lying triplet excited state. The electrochemical release of CO showed a greater efficiency for the chromium complex when compared to the tungsten.

    Item Type: Article
    Keywords: photochemistry; electrochemically induced CO-loss; [(CO)5MC(OMe)Me](M = Cr or W); low-temperature matrix isolation; picosecond infrared spectroscopy; cyclic voltammetry; time-dependent density functional theory;
    Academic Unit: Faculty of Science and Engineering > Computer Science
    Item ID: 7810
    Identification Number: https://doi.org/10.1039/c5dt01568e
    Depositing User: Dr. Denise Rooney
    Date Deposited: 25 Jan 2017 15:04
    Journal or Publication Title: Dalton Transactions
    Publisher: Royal Society of Chemistry
    Refereed: Yes
    URI:
    Use Licence: This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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