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Photo-isomerisation of alkenyl complexes of platinum(ii) : structural, spectroscopic, kinetic and computational investigations
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Barone, Carmen R., Coletti, Cecilia, McQuitty, Ruth J., Farrer, Nicola J., Lorusso, Giuseppe, Maresca, Luciana, Marrone, Alessandro, Natile, Giovanni, Pacifico, Concetta, Parsons, Simon, Re, Nazzareno, Sadler, P. J. and White, Fraser J. (2013) Photo-isomerisation of alkenyl complexes of platinum(ii) : structural, spectroscopic, kinetic and computational investigations. Dalton Transactions, Volume 42 (Number 19). pp. 6840-6851. doi:10.1039/c3dt32354d ISSN 1477-9226.
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Official URL: http://dx.doi.org/10.1039/C3DT32354D
Abstract
In this work UVA and blue light have been used to study photo-isomerisation about the C[double bond, length as m-dash]C double bond in complexes of the type [PtCl(–CH[double bond, length as m-dash]CHAr)(tmeda)] [Ar = C6H5, (E)-2a; 4-CH3O–C6H4, (E)-2b; 3-NO2–C6H4, (E)-2c; and 3-CH3O–C6H4, (E)-2d]. The progress of the reaction has been monitored by NMR spectroscopy following irradiation of the NMR sample. The NMR data have been complemented with X-ray diffractometric analysis of compounds (E)-2a–c and (Z)-2a. The kinetic data clearly indicate that a monomolecular mechanism is operating with the energy of the irradiating light influencing the rate of isomerisation but not the equilibrium composition, which is only slightly in favour of the Z isomer. DFT and TD-DFT theoretical investigations have been carried out to elucidate the nature of the main electronic transitions in the UV-Vis region and the mechanism of the photo-isomerisation reaction appears to proceed through a C[double bond, length as m-dash]C bond twist process similar to that involved in purely organic molecules such as stilbene. In the Z isomer, one ortho proton of the phenyl group can come close to platinum (PtHortho distance of 2.632 Å in (Z)-2a). In the case of 2c, the difference in chemical shift between the two ortho protons varies from 3.30 ppm in the Z isomer, where interaction with Pt is possible, to 0.60 ppm in the E isomer, where such interaction cannot take place. The analysis of the DFT orbitals indicates that the most shifted Hortho is that with a greater positive charge, pointing to an H-bond type of interaction.
Item Type: | Journal Article | ||||
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
Journal or Publication Title: | Dalton Transactions | ||||
Publisher: | Royal Society of Chemistry | ||||
ISSN: | 1477-9226 | ||||
Official Date: | 20 February 2013 | ||||
Dates: |
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Volume: | Volume 42 | ||||
Number: | Number 19 | ||||
Page Range: | pp. 6840-6851 | ||||
DOI: | 10.1039/c3dt32354d | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access |
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