Abstract
The thermodynamics of complex formation between gold(I) and the ligands tricyclohexylphosphine, triphenylamine, -phosphine, -arsine, and -stibine has been determined in pyridine solution by potentiometric and calorimetric measurements. As expected, the very soft gold(I) displays a more marked stability (b)-sequence N ⪡ P > As > Sb than its lighter, and less soft, congener silver(I). Like all complexes of these ligands so far studied, the present ones are strongly enthalpy stabilized while the entropy changes are generally unfavourable. The stepwise entropy changes show quite peculiar differences between the various ligands, however. The thermodynamics of these complexes is in striking contrast to that of the gold(I) halido complexes in pyridine which are strongly entropy stabilized, while the enthalpy changes are small.
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