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

Abstract

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, [(Ph3P)2Pt(η2‐C2H4)], yielded the (disulfenato)PtII complex 18 and the (sulfenato–thiolato)PtII 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)PtII complex 19, while the oxidation with CF3CO3H 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/CF3CO2H provided 18 and that with DMD/PhCO2H gave 19. Oxidation of 14 with an excess amount of DMD yielded the (disulfonato)PtII complex 20.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Reaction of 3,3,5,5‐Tetraphenyl‐1,2,4‐trithiolane with Pt0(bisphosphane)(η2‐nbe) Complexes Bearing Bridged Bisphosphane Ligands with Various Bite Angles

“…The best proof for the presence of dithiiranes as reactive intermediates is the interception with the Pt 0 (PPh 3 ) 2 complex fragment to form stable dithiolato complexes 5b,6e,6f,7. In contrast, the oxidative addition of the Pt 0 (PPh 3 ) 2 complex fragment into the sulfur–sulfur bond of 1,2,4‐trithiolanes does not allow the generation of thiosulfines by cycloreversion from this common type of precursor molecule 7a,8.…”

Photochemical Oxidation of Pt(IV)Me3(1,2-diimine) Thiolates to Luminescent Pt(IV) Sulfinates

“…The Pt–S bonds are all of similar lengths; however, the Pt–S bonds in sulfinate complexes ( 12 , 17 , 26 – 29 ) are shorter that those in the other complexes. A search of the Cambridge Crystallographic Data Centre for structures containing the Pt-SO 2 R unit found only 23 reports of this substructure, of these 20 were cyclic − (i.e., contained a chelating O 2 S^D unit, D = donor atom), meaning that only three unsupported Pt-SO 2 bonds have previously been characterized, and there were no Pt­(IV) sulfinates reported.…”

ChemInform Abstract: The Topotactic Reduction of Sr3Fe2O5Cl2—Square Planar Fe(II) in an Extended Oxyhalide.

“…Almost 20 years ago, Ishii, Nakayama, and co‐workers reported the first synthesis of isolable, sterically crowded dithiiranes as well as their corresponding 1‐ S ‐oxides 5. 6 They demonstrated that these compounds were highly reactive towards [Pt 0 (PPh 3 ) 2 (η 2 ‐C 2 H 4 )] ( 5 ) and they characterized the isolated dithiolato complexes, as well as thiolato–sulfenato complexes, by X‐ray diffraction 6a. 7a–c A similar reactivity was observed for naphtha‐[1,8 cd ][1,2]dithiols towards Pt 0 –olefin complexes 7d.…”