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Issue 42, 2012
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Photoactivated linkage isomerism in single crystals of nickel, palladium and platinum di-nitro complexes – a photocrystallographic investigation

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Abstract

Low temperature, single crystal photocrystallographic studies have been carried out on four square planar Group 10 complexes [Ni(PEt3)2(NO2)2] 1, [Pd(PPh3)2(NO2)2] 2, [Pd(AsPh3)2(NO2)2] 3 and [Pt(PPh3)2(NO2)2] 4, in which the two nitro groups adopt the trans configuration. Irradiation with UV light, at 100 K, of single crystals of complexes 1–3 photoisomerise from the η1-NO2 nitro form to the η1-ONO nitrito form occurred. Complex 1 underwent 25% conversion to the nitrito form before crystal decomposition occurred. 2 and 3 underwent 46% and 39% conversion, respectively, to the nitrito form when a photostationary state was reached. While under the same experimental conditions 4 showed no isomerisation. The photocrystallographic results can be correlated with the results of DFT calculations and with the observed trends in the solution UV/visible absorption spectroscopy obtained for these complexes. The results suggest that while steric factors in the isomerization processes are important there may also be a kinetic effect relating to the lability of the metal involved.

Graphical abstract: Photoactivated linkage isomerism in single crystals of nickel, palladium and platinum di-nitro complexes – a photocrystallographic investigation

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Supplementary files

Article information


Submitted
12 Feb 2012
Accepted
10 May 2012
First published
10 May 2012

Dalton Trans., 2012,41, 13173-13179
Article type
Paper

Photoactivated linkage isomerism in single crystals of nickel, palladium and platinum di-nitro complexes – a photocrystallographic investigation

M. R. Warren, S. K. Brayshaw, L. E. Hatcher, A. L. Johnson, S. Schiffers, A. J. Warren, S. J. Teat, J. E. Warren, C. H. Woodall and P. R. Raithby, Dalton Trans., 2012, 41, 13173 DOI: 10.1039/C2DT30314K

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