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 hemolytic 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. © 1989.213283291Magee, Hill, The Analytical Chemistry of Metal Dithiocarbamate Complexes (1985) Reviews in Analytical Chemistry, 8, p. 5Coucouvanis, The Chemistry of the Dithioacid and 1,1-Dithiolate Complexes (1970) Progr. Inorg. 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