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Photooxidation of Platinum(II) Diimine Dithiolates

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. https://resolver.caltech.edu/CaltechAUTHORS:20180521-110903590

[img] PDF (Details of data collection and structure refinement and tables of atomic coordinates, bond distances and angles, anisotropic displacement parameters, and hydrogen atom positions for Pt(bpy)(bdt), Pt(bpy)(bdtO2), and Pt(bpy)(bdtO4) (26 pages)) - Supplemental Material
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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.


Item Type:Article
Related URLs:
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https://doi.org/10.1021/ja9723803DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/ja9723803PublisherSupporting Information
ORCID:
AuthorORCID
Gray, Harry B.0000-0002-7937-7876
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
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:22 Nov 2019 09:58

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