Sequential Photooxidation of a Pt(II) (Diimine)cysteamine Complex: Intermolecular Oxygen Atom Transfer versus Sulfinate Formation

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• 作者：Dong Zhang ; Ye Bin ; Lorillee Tallorin ; Florence Tse ; Blanca Hernandez ; Errol V. Mathias ; Timothy Stewart ; Robert Bau ; Matthias Selke
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：February 18, 2013
• 年：2013
• 卷：52
• 期：4
• 页码：1676-1678
• 全文大小：184K
• 年卷期：v.52,no.4(February 18, 2013)
• ISSN：1520-510X

文摘

The thiolato complex [platinum(II) (bipyridine)(N,S-aminoethanethiolate)]⁺Ch^{鈥?/sup> (1) undergoes sequential reactions with singlet oxygen to initially form the corresponding sulfenato complex [platinum(II) (bipyridine)(N,S(鈺怬)-aminoethansulfenate)]+ (2) followed by a much slower reaction to the corresponding sulfinato complex. In contrast with many platinum dithiolato complexes, 1 does not produce any singlet oxygen, but its rate constant for singlet oxygen removal (k_T) is quite large (3.2 脳 107 M鈥? s鈥?) and chemical reaction accounts for ca. 25% of the value of k_T. The behavior of 1 is strikingly different from that of the complex platinum(II) (bipyridine)(1,2-benzenditholate) (4). The latter complex reacts with 1O₂ (either from an external sensitizer or via a self-sensitized pathway) to form a sulfinato complex. These two very different reactivity pathways imply different mechanistic pathways: The reaction of 1 with 1O₂ must involve O鈥揙 bond cleavage and intermolecular oxygen atom transfer, while the reactive intermediate in complex 4 collapses intramolecularly to the sulfinato moiety.}