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.
Reaction of the title bicyclic disulfide 16 with [(Ph3P)2Pt(eta2-C2H4)] (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.
Ishii
Akihiko
A
Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Saitama, Saitama 338-8570, Japan. ishiiaki@chem.saitama-u.ac.jp
Kashiura
Satoshi
S
Hayashi
Yuichi
Y
Weigand
Wolfgang
W