Connick, William B. and Gray, Harry B. (1997) Photooxidation of Platinum(II) Diimine Dithiolates. Journal of the American Chemical Society, 119 (48). pp. 11620-11627. ISSN 0002-7863. doi:10.1021/ja9723803. https://resolver.caltech.edu/CaltechAUTHORS:20180521-110903590
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Abstract
The violet color of Pt(bpy)(bdt) (bpy = 2,2‘-bipyridine; bdt = 1,2-benzenedithiolate) is due to a Pt/S → diimine charge-transfer transition; the emission originates from the corresponding triplet state (τ = 460 ns). Photochemical oxidation of Pt(bpy)(bdt) occurs in the presence of oxygen in N,N-dimethylformamide, acetonitrile, or dimethyl sulfoxide solution; the reaction has been investigated by ^1H NMR and UV−visible absorption spectroscopy. Singlet oxygen produced by energy transfer from the excited complex is implicated as the active oxygen species, in sequential formation of sulfinate, Pt(bpy)(bdtO_2), and disulfinate, Pt(bpy)(bdtO_4), products. Both products have been characterized by X-ray crystallography. The rate of photooxygenation is strongly dependent on water concentration, and transient absorption spectra are consistent with the formation of at least one intermediate. As a whole, our data suggest that the photooxidation chemistry of platinum(II) diimine dithiolates is similar to that of organic sulfides.
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| Additional Information: | © 1997 American Chemical Society. Received July 16, 1997. We thank A. J. Di Bilio, M. G. Hill, L. M. Henling, V. M. Miskowski, and J. R. Winkler for expert technical assistance and helpful discussions. This work was supported by the National Science Foundation. | |||||||||
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| Issue or Number: | 48 | |||||||||
| DOI: | 10.1021/ja9723803 | |||||||||
| Record Number: | CaltechAUTHORS:20180521-110903590 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180521-110903590 | |||||||||
| Official Citation: | Photooxidation of Platinum(II) Diimine Dithiolates. William B. Connick and Harry B. Gray. Journal of the American Chemical Society 1997 119 (48), 11620-11627. DOI: 10.1021/ja9723803 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 86499 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Tony Diaz | |||||||||
| Deposited On: | 21 May 2018 18:14 | |||||||||
| Last Modified: | 15 Nov 2021 20:39 |
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