Resonance Induced Properties in Monothiocarbamates Derived from Aromatic Amines: Comparison of the Coordination Chemistry of Indole and Indoline Monothiocarbamates
The syntheses of two new monothiocarbamate ligands and selected transition element complexes of each are reported. The complexes of indoline-N-carbothioate (intc) prepared are: NiL2·1.5H2O, ZnL2, NiL2·2py, ZnL2·2py. The complexes of indole N-carbothioate (iltc) are: NiL′2, ZnL′2, Cul′. IR spectral results support a bidentate ligand behavior for both new monothiocarbamates except in ZnL2·2py. Comparison of the IR spectral features of bis(indolylcarbamoyl)-disulfide with that of coordinated indole-N-carbothioate allowed an assignment of the C-S and C-O vibrational frequencies. Evidence for differences in major resonance contributions to the electronic structures of each new ligand are presented. The crystal structure of thebis(indolylcarbamoyl)disulphide is also presented and a comparison is made to pyrrole-N-carbothioate, another aromatic amine monothiocarbamate. The disulphide crystallizes in the centrosymmetric monoclinic space group P21/c with a = 15.64(4)Å, b = 5.228(1)Å,c = 19.271(7)Å, β = 97.20(2)°, V = 1564(1)Å3, d(obsd)(calcd) = (1.50)(1.52) for a molecular weight = 356.1 and Z = 4. Diffraction data were collected with a Syntex Pdiffractiometer with CuKα radiation. Least squares refinement resulted in Rf = 7.0% for all 1213 non zero reflections have (I)> 3σ(I).
Bereman, Robert D.; Baird, Donald M.; Bordner, Jon; and Dorfman, Jay R., "Resonance Induced Properties in Monothiocarbamates Derived from Aromatic Amines: Comparison of the Coordination Chemistry of Indole and Indoline Monothiocarbamates" (1983). Chemistry and Physics Faculty Articles. 26.