The synthesis of the compounds of general formula [Mo2O(S2CNR)2(YC6H4CXN2)2]-Sol, X = S and O, Y = H and Cl, and Sol = CH2C12 and CHC13, is reported. The compounds were characterized by elemental analyses and infrared, electronic, and 1H NMR spectroscopy. The 1H NMR spectra exhibited a number of alkyl resonances, suggesting that the dithiocarbamate ligands are nonequivalent. The molecular structures of the compounds [Mo2O(S2CNEt2)2(C6H5CON2)2].CH2Cl2 and [Mo2O(S2CNEt2)2(ClC6H4CSN2)2].CHCl3 were revealed in single-crystal X-ray diffraction studies. The structures are analogous and shown to be asymmetric dinuclear complexes with bridging benzoyldiazendio or thiobenzoyldiazenido ligands. The nonplanar Mo2N2 rhombus is common to both structures and exhibits a nearly identical geometry in the two derivatives. The geometries about the square-pyramidal Mo2 sites are also constant. The Mol sites are approximately trigonal prismatic, the coordination polyhedra constrained by the geometric requirements of sulfur vs. oxygen coordination. Voltammetric studies of the dimers indicate a reversible one-electron reduction, followed by an irreversible cathodic process at more negative potentials. The redox behavior of the dimers is discussed and contrasted with that of the symmetrical dimers Mo2O3(S2CX)4, X = -NR2, -OR, and -SR.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry