Thermochemical properties of chelates of di-n-butyldithiocarbamate with phosphorus-group elements

Article abstract of DOI:10.1016/0021-9614(89)90018-9

The standard molar enthalpies of formation of crystalline tris(di-n-butyldithiocarbamato)E(III), (E = P, As, Sb, or Bi), determined at 298.15 K by solution-reaction calorimetry, are -(705.5 +/- 7.3), -(443.1 +/- 5.4), -(526.2 +/- 2.5), and -(530.7 +/- 5.5) kJ*mol^-1, respectively.The enthalpies of sublimation: (136 +/- 3), (128 +/- 3), (179 +/- 3), and (202 +/- 3) kJ*mol^-1, were estimated.From the enthalpies of formation of the gaseous complexes, the homolytic and heterolytic mean standard molar element-sulphur bond enthalpies were calculated.These values are correlated with element-sulphur bond distances, and a larger phosphorus- sulphur bond enthalpy reflects a better overlap of d orbitals in bonding formation.