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Rearrangement of a (Dithiolato)platinum(II) Complex Formed by Reaction of Cyclic Disulfide 7,8‐Dithiabicyclo[4.2.1]nona‐2,4‐diene with a Platinum(0) Complex: Oxidation of the Rearranged (Dithiolato)platinum(II) Complex
Author(s) -
Ishii Akihiko,
Kashiura Satoshi,
Hayashi Yuichi,
Weigand Wolfgang
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200601681
Subject(s) - platinum , chemistry , dimethyldioxirane , oxidative addition , diene , yield (engineering) , medicinal chemistry , sulfur , reductive elimination , disulfide bond , photochemistry , polymer chemistry , stereochemistry , organic chemistry , catalysis , materials science , biochemistry , natural rubber , metallurgy
Reaction of the title bicyclic disulfide 16 with [(Ph 3 P) 2 Pt(η 2 ‐C 2 H 4 )] ( 2 ) yielded the corresponding (dithiolato)platinum(II) complex 17 by oxidative addition. The initial product 17 isomerized at room temperature in a [1,5]‐sulfur rearrangement to give another (dithiolato)platinum(II) complex 18 in high isolated yield. Oxidation reactions of 18 with dimethyldioxirane (DMD) provided (sulfenato‐thiolato)platinum(II) 23 , (sulfinato‐thiolato)platinum(II) 24 , (sulfenato‐sulfinato)platinum(II) 25 , and (disulfinato)platinum(II) 26 complexes, the structures of which were elucidated by NMR spectroscopy and X‐ray crystallography. The oxidation process took place regioselectively in the first step and chemoselectively in the second. The selectivities are discussed.