Syntheses, crystal structure and spectroscopic characterization of new platinum(II) dithiocarbimato complexes

The reaction of 4-iodobenzenesulfonamide or 4-fluorobenzenesulfonamide with CS₂ and KOH in dimethylformamide yielded the potassium N-R-sulfonyldithiocarbimates, K₂(RSO₂NCS₂) [R = 4-IC₆H₄ (1) and 4-FC₆H₄ (2)]. These salts reacted with K₂[PtCl₄] in water/methanol to yield complex anions bis(N-R-sulfonyldithiocarbimato)platinate(II), which were isolated as their tetrabutylammonium salts, (Bu₄N)₂[Pt(RSO₂NCS₂)₂] [R = 4-IC₆H₄ (3) and 4-FC₆H₄ (4)]. The structures of 2–4 were determined by X-ray crystallography. The Pt²⁺ in both complexes 3 and 4 lies at the inversion centre and the PtS₄ moiety has a distorted square-planar configuration. The compounds were also characterized by IR, ¹H NMR and ¹³C NMR spectroscopies, and elemental analyses. The molar conductance data are consistent with the fact that 3 and 4 are dianionic complexes.     

Synthesis, spectroscopic characterization and vulcanization activity of a new compound containing the anion bis(4-methylphenylsulfonyldithiocarbimato)zincate(II)

A new compound of the formula: (Bu₄N)₂[Zn(4-CH₃C₆H₄SO₂NCS₂)₂] (Bu₄N = tetrabutylammonium cation) was obtained by the reaction of CH₃C₆H₄SO₂NCS₂K₂ · 2H₂O with zinc(II) acetate dihydrate and tetrabutylammonium bromide in dimethylformamide. The elemental analyses of C, H, N and Zn are consistent with the proposed formula. The IR data point to the formation of a zinc(II)-bis(dithiocarbimato) complex. The ¹H NMR and ¹³C NMR spectra showed the expected signals for the tetrabutylammonium cation and the dithiocarbimato moiety. This compound was evaluated as for the vulcanization activity and compared to the commercial accelerators CBS, MBTS and TMTD. These studies showed that the zinc(II)-ditiocarbimates are a new class of rubber vulcanization accelerators, worth of further investigation.     

Syntheses, characterization, crystal structure and antifungal activity of four tetraphenylphosphonium bis(N-R-sulfonyldithiocarbimato)zincate(II) salts

Four new compounds of the general formula: (Ph₄P)₂[Zn(RSO₂NCS₂)₂] where Ph₄P = tetraphenylphosphonium cation, R = 4-FC₆H₄ (1), 4-ClC₆H₄ (2), 4-BrC₆H₄ (3) and 4-IC₆H₄ (4), were obtained by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO₂NCS₂K₂) with zinc(II) acetate dihydrate in dimethylformamide. All compounds crystallize in the centrosymmetric space group of the triclinic system. The compounds 2, 3 and 4 are isostructural but compound 1 crystallizes as hemihydrate. The elemental analyses and the IR, ¹H NMR and ¹³C NMR data for 1-4 are consistent with the formation of bis(dithiocarbimato)zinc(II) complexes. These compounds are active against the phytopathogenic fungus Colletotrichum gloeosporioides.