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
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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