Thio derivatives of β-diketones and their metal chelates. V. Acid dissociation constants of some Monothio-β-diektones and stability constants of anickel(II) and a copper(II) chelate

Abstract

The acid dissociation constants (PKD) of the monothio derivatives of acetyl-acetone, dibenzoylmethane, and 3,3,3-trifluoro-1-(2- thenoyl)acetone, viz. 4-mercap-topent-3-en-2-one (I), 3-mercapto-1,3- diphenylprop-2-en-1-one (II), and 1,1,1-trifluoro-4-mercapto-4-(2- thienyl)but-3-en-2-one (III), were determined in dioxan/water solutions with varying mole fraction (n2) of dioxan. Over a range of n2 from 0.18 to 0.44 the values of pKD were found to vary linearly with n2 as given by the equations: (I) pKD = 5.7+12.0n2; (II) pKD = 7.0+10.9n2; (III) pKD = 3.55 + 9.2n2. The thio derivatives (I), (II), and (III) have pKD values 2.0-2.7 log units lower than their oxygen analogues. The logarithm of the stability constants (log β2) for the nickel(II) and copper(II) complexes of (II) were found to be 21.7 and 22.2, respectively. For both complexes K2 > K1. Comparison with the stability constants of the dibenzoylmethane complexes shows that for nickel(II) the complex of the monothio-β-diketone is more stable than that of the β-diketone while the converse is true for copper(II).