Thermochemical data on adducts of cyclic ureas and copper chloride: the resemblance to biological systems

摘要

Adducts of the general formula CuCl2. 4L (L: ethyleneurea (eu), ethylenethiourea (etu) and propyleneurea (pu)) were synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetry and calorimetry. The infrared results showed that eu and pu coordinate through carboxylic oxygen atoms, whereas etu uses the nitrogen atom to bond the cation. Thermal degradation of adducts starts at 130, 160 and 140 degreesC, respectively, and is reflected by a one stage mass loss. Decomposition temperatures correlate, to some extent, with metal-ligand bond strength. The standard enthalpies of the reaction: CuCl2(c) + 4L(c) = CuCl2. 4L(c) in the condensed phase (A,,He) were determined by reaction-solution calorimetry. The following values were obtained: -42.50 +/- 0.92; -48.76 +/- 0.66 and -43.64 +/- 0.51 kJ mol(-1) for eu, etu and pu adducts, respectively. Using Delta H-r(m)theta values and auxiliary enthalpies of sublimation of copper chloride and adducts, the enthalpies of decomposition (Delta H-D(m)theta), lattice enthalpies (Delta H-M(m)theta), enthalpies of reaction in the gaseous phase (Delta H-g(m)theta) and the mean metal- ligand bond enthalpies (D ) were calculated to be: Delta H-D(m)theta = 377.3 +/- 7,7; 518.0 +/- 8.4; 400.8 +/- 10.0, Delta H-M(m)theta = 552.0 +/- M M 7.7;692.7 +/- 8.5;575.5 +/- 10.1; Delta H-g(m)theta = 468.3 +/- 8.0; 575.4 +/- 8.8; 486.2 +/- 10.4 and D = 117.1 +/- 2.0; 143.8 +/- 2.2; 121.6 +/- 2.6, for eu, etu and pu adducts, respectively. (C) 2001 Elsevier Science B.V. All rights reserved. [References: 32]