Preparation of 3,3‐Di‐ tert ‐butylthiirane trans ‐1,2‐Dioxide and Its Reaction with a Platinum(0) Complex To Give a (Disulfenato)platinum(II) Complex: Regioselectivity of the Oxidation of a Related (Sulfenato–thiolato)platinum(II) Complex

A three‐membered vic ‐disulfoxide, 3,3‐di‐ tert ‐butyldithiirane trans ‐1,2‐dioxide ( 8 ), was synthesized by oxidation of the corresponding dithiirane 1‐oxide 15 in high yield. Treatment of 8 and 15 with a platinum(0) complex, [(Ph 3 P) 2 Pt(η 2 ‐C 2 H 4 )], yielded the (disulfenato)Pt II complex 18 and the (sulfenato–thiolato)Pt II complex 14 , respectively, in high yields. Oxidation of the sulfenato–thiolato complex 14 with an acetone solution of dimethyldioxirane (DMD) took place at the sulfenato sulfur atom to yield the (sulfinato–thiolato)Pt II complex 19 , while the oxidation with CF 3 CO 3 H occurred at the thiolato‐sulfur atom leading to the disulfenato complex 18 . Oxidation of 14 with MCPBA formed both 18 and 19 . The position of oxidation on 14 with DMD was dependent on the acidity of a coexisting acid. Thus, oxidation of 14 with DMD/CF 3 CO 2 H provided 18 and that with DMD/PhCO 2 H gave 19 . Oxidation of 14 with an excess amount of DMD yielded the (disulfonato)Pt II complex 20 .(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)