Sulfoxide Carbon−Sulfur Bond Activation

Abstract

The alkynylsulfoxide, TMSCCSO(p-tolyl) (TMS = trimethylsilyl, tolyl = C6H4Me), undergoes reaction with (eta5-C5H5)Co(PPh3)2 at room temperature to give the cobaltosulfoxide complex, (C5H5)Co(PPh3)(eta1-CCTMS)[eta1-(S)-SO(p-tolyl)], which was characterized by X-ray crystallography. Exposure of this cobaltosulfoxide complex to oxygen gas leads to the formation of the corresponding metallosulfone complex, (C5H5)Co(PPh3)(eta1-CCTMS)[eta1-(S)-SO2(p-tolyl)], which was characterized by X-ray crystallography. Alternatively, in solution at room temperature, the metallosulfoxide is converted to a 1:4 mixture of the equatorial-equatorial and equatorial-axial bridging cobalt-thiolato dimers, {(C5H5)Co[mu-S(p-tolyl)]}2, respectively. The equatorial-equatorial isomer was characterized by X-ray crystallography.

Metal and Ligand Control of Sulfenate Reactivity: Arene Ruthenium Thiolato‐Mono‐S‐Oxides

“…oxygen bond is longer [6,9,14,18] than those in sulfinates; sulfenates have a negatively charged oxygen atom that forms hydrogen bonds [4,19] and can be protonated. [5,6] Nevertheless, the oxygen atom in sulfenates can exchange with water oxygen atoms and provides some catalytic activity in nitrile hydrolysis.…”

“…[3,10] One important difference between thiolato, sulfenato, and sulfinato ligands is the ability of sulfenates to exert high trans effects. [11][12][13] Sulfenates can be either oxidized [14] or reduced. [6,15] Notably, the corresponding free ligands (sulfenic acids) are unstable and highly reactive, [16,17] and the sulfuroxygen bond is longer [6,9,14,18] than those in sulfinates; sulfenates have a negatively charged oxygen atom that forms hydrogen bonds [4,19] and can be protonated.…”

Synthesis and characterization of Pd(IMe)2, and its reactivity by C–S oxidative addition of DMSO

“…Well-defined CeS bond cleavage in sulfoxides by transition metals reported previously: (a)[28],(b) [7c].Scheme 7. Sulfinyl/sulfenate isomerization in 3 (SMD-B3PW91/BS II//BS I).…”

PRELIMINARY RESULTS OF THE REACTION OF CYCLOTRIMERIZATION OF PHENYLACETYLENE [2+2+2] CATALYZED BY [(Cp*)Co(Indene)] COMPLEX

“…Although the mechanism of this reaction has been the subject of multiple experimental and computational studies, it is not as yet fully elucidated. After pioneering semiempirical [21,22] and ab initio efforts [23], a more detailed DFT analysis was reported by Albright and co-workers in 1999 [24]. In that work are presented [(Cp) Co(PH 3 ) 2 ] as a model precatalyst and ethyne as a model reagent.…”