Issue 11, 2003
From the journal:

Dalton Transactions

Monodentate and bridging coordination of 2,5-dimercapto-1,3,4-thiadiazolate to a (2,2′:6′,2″-terpyridine)platinum(ii) center†

Hidenori Tannai,a   Kiyoshi Tsuge,*a   Yoichi Sasaki,*a   Osamu Hatozakib  and  Noboru Oyamab  

* Corresponding authors

a Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan
E-mail: ysasaki@sci.hokudai.ac.jp

b Department of Applied Chemistry, Faculty of Technology, Tokyo University of Agriculture and Technology, Naka-cho, Tokyo 184-8588, Japan

Abstract

A series of mono- and di-nuclear platinum complexes, [Pt(trpy)(McMT)](PF6) (1), [Pt(trpy)(DMcTH)](PF6) (2) and [(Pt(trpy))2(DMcT)](PF6)2 (3) has been synthesized by the reaction of [Pt(trpy)(OH)](PF6) with mercapto- and dimercapto-thiadiazoles (trpy = 2,2′:6′,2″-terpyridine, McMTH = 2-mercapto-5-methyl-1,3,4-thiadiazole, DMcTH2 = 2,5-dimercapto-1,3,4-thiadiazole). The X-ray structure determinations revealed that the mercaptothiadiazoles coordinate to the platinum centers as κ1S-thiolate forms in all three complexes. Mononuclear DMcT–Pt complex 2 has a free thioamide group which is responsible for the formation of a hydrogen-bonded dimeric structure in the solid state. The complexes 1 and 2 show LLCT emissions in the solid state, whereas 3 is non-emissive. Cyclic voltammograms of the three complexes in DMF commonly show two reduction processes at ca. −0.7 V and −1.3 V based on the {Pt(trpy)}2+ units. Complex 2 further shows the oxidation of a free thioamide group at 0.32 V (vs. Ag/AgCl) on the addition of Et3N.

Graphical abstract: Monodentate and bridging coordination of 2,5-dimercapto-1,3,4-thiadiazolate to a (2,2′:6′,2″-terpyridine)platinum(ii) center

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Article information

DOI
https://doi.org/10.1039/B301390C
Article type
Paper
Submitted
04 Feb 2003
Accepted
16 Apr 2003
First published
07 May 2003

Dalton Trans., 2003, 2353-2358

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Monodentate and bridging coordination of 2,5-dimercapto-1,3,4-thiadiazolate to a (2,2′:6′,2″-terpyridine)platinum(II) center

H. Tannai, K. Tsuge, Y. Sasaki, O. Hatozaki and N. Oyama, Dalton Trans., 2003, 2353 DOI: 10.1039/B301390C

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