Sequential Photooxidation of a Pt(II) (Diimine)cysteamine Complex: Intermolecular Oxygen Atom Transfer versus Sulfinate Formation
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https://figshare.com/articles/dataset/Sequential_Photooxidation_of_a_Pt_II_Diimine_cysteamine_Complex_Intermolecular_Oxygen_Atom_Transfer_versus_Sulfinate_Formation/2442364
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资源简介：
The thiolato complex [platinum(II) (bipyridine)(N,S-aminoethanethiolate)]+Ch– (1) undergoes sequential reactions with
singlet oxygen to initially form the corresponding sulfenato complex
[platinum(II) (bipyridine)(N,S(O)-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 (kT) is quite large (3.2 × 107 M–1 s–1) and chemical reaction accounts for ca. 25%
of the value of kT. 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–O bond cleavage and intermolecular oxygen
atom transfer, while the reactive intermediate in complex 4 collapses intramolecularly to the sulfinato moiety.
创建时间：
2016-02-19
