New Chemical Reactivity in Aromatic Dithiocarbamate and Monothiocarbamate Ligands: Syntheses of Mo2L4·2THF (L = Pyrrole or indole monothiocarbamate or pyrrole dithiocarbamate) and Mo2L4 (L = indoline monothiocarbamate)

The reactions between Mo2(C2H3O2)4 and several new dithio- and monothiocarbamates have been studied. The first example of a dimolybdenum compound of a dithiocarbamate with the “molybdenum acetate” structure is reported (Mo2L4·2THF; L = pyrrole dithiocarbamate). In addition, the synthesis of Mo2L′4·2THF (L′ = pyrrole monothiocarbamate, indole monothiocarbamate, indole dithiocarbamate) and Mo2L″4 (L″ = indoline monothiocarbamate) are reported. A discussion of the unique stabilization of the dithiocarbamate bridge by “aromatic” dithio- and monothiocarbamates is presented

Coordination Chemistry of New Sulfur Containing Ligands -- 21. Selected Transition Element Complexes of Pyrrole-n-carbothioate: A New Type of Monothiocarbamate Ligand

Two new monothiocarbamate ligands have been prepared and their coordination chemistry has been investigated. Potassium pyrrole-N-carbothioate, prepared from potassium pyrrolate and COS, is a white, air sensitive solid which reacts with NiBr2 and PdBr2 to yield 2:1 ligand to metal compounds. The Ni compound has been characterized by IR spectroscopic studies as well as a detailed magnetic study. Results show that the Ni(II) compound is a dimer with one paramagnetic and one diamagnetic Ni center. The magnetic moment is 2.53 ± 0.05 B.M. per Ni atom in the range 9.7–66.6 K. The Pd compound of the pyrrole-N-carbothioate ligand is apparently monomeric and four-coordinate. This is the first example of a simple bis-bidentate monothiocarbamate complex of Pd(II). The structure and bonding in these new compounds is discussed in terms of the resonance structures of the ligands. Potassium indoline-N-carbothioate reacts with CuBr2 to yield the disulfide, bis(indolinecarbomoyl)disulfide and copper(I)

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)\u3e 3σ(I)