Sulfenato, Thiosulfinato, and Thiosulfonato Transition Metal Complexes

Abstract

The synthesis and coordination chemistry of sulfenic, thiosulfinic, and thiosulfonic acid anions are reviewed. Different approaches, which yield the platinum(I1) and ruthenium(I1) complexes containing the anionic sulfur(0), sulfur(II), and sulfur(1V) oxid ligands, are described. The oxidative addition of thiosulfinates or N-sulfinyl phthalimides to platinum(0) complexes L2Pt(C2H4) [L = PPh3, 112 PPh2CH2CH2PPh2, 1/2 (R,R)-( -1-DIOP, 1/2 (C5H4PPh2)Fe(C5H4PPh2) leads to sulfenato complexes; those of N-thiosulfinyl phthalimides or trisulfid 1-oxides afford the thiosulfinato complexes. Moreover, the reactions of CpRu(PPh,)(L)(SH) (L = CO, PPh3) with Nsulfinyl phthalimides forming the thiosulfinato moiety, are reported. The spectroscopic, structural and chemical properties of these complexes are discussed.

A Two-Step Palladium-Catalyzed Coupling Scheme for the Synthesis of Ferrocene-Labeled Amino Acids

“…Since disulfide bonds play a pivotal structural role in many enof ECD, compounds 7 and 8 were investigated electrochemically. Both groups of compounds show a reversible zymes, [68] and insertion reactions into disulfide bonds are well documented for Pt complexes, [69,70] the obvious queswave in the cyclic voltammogram (CV) at ϩ173 mV (7) and between ϩ187 and ϩ197 mV (8) vs. ferrocene/ferrocenium. tion needs to be answered as to whether our coupling would work for cystine derivatives.…”

Platinum Complexes of Dibenzo[1,2]Dithiin, Dibenzo[1,2]Dithiin Oxides and Related Polyaromatic Hydrocarbon Ligands

“…[13] Thiolato-sulfenato complexes have been obtained from oxidative addition reactions of cyclic thiosulfinates with Pt 0 precursors [14][15][16][17][18][19][20] and dithiirane 1-oxides [21] or by the mono-oxidation of the corresponding dithiolate complex, for example, the dinuclear iron complexes [{(OC) 3 …”

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

“…This 1 J Pt,P coupling constant value is comparable to those for phosphorus atoms trans to the S=O groups. [12][13][14][15][16][17][18][19][20][21][22][23][24] The absorption due to the S=O stretching vibration is observed at 1097 cm -1 in the IR spectrum, which is close to those of the reported (sulfenato)Pt II complexes. [12][13][14][15][16][17][18][19][20][21][22][23][24] Recrystallization of 18 from benzene provided single crystals (yellow prisms) suitable for X-ray crystal analysis, and the structure was determined unambiguously (Figure 2).…”

“…The PtO 2 S 2 C six-membered ring has a twist conformation in the crystalline state. While the two tert-butyl groups are equivalent in the 13 C NMR spectrum, they are nonequivalent in the 1 H NMR spectrum. In the 31 P NMR spectrum, a singlet with satellite signals from the 195 Pt isotope is observed at δ = 7.10 ppm ( 1 J Pt-P = 4157 Hz).…”

“…at -20°C proceeded slowly to give 8 in 31 % yield together with sulfine 16 (6 %) and the starting compound 15 (63 %) ( 1 H NMR integral ratio). In the 1 H NMR and 13 C NMR spectra, the two tert-butyl groups of 1,2-dioxide 8 are equivalent, and in the 13 C NMR spectrum, the dithiirane carbon resonated at δ = 105.9 ppm, shifted to the lower field by 19.6 ppm than that of the 1-oxide 15 (δ = 86.3 ppm).…”