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Isokinetic relationships at the thermal decomposition of tetranuclear copper(II)-complexes

✍ Scribed by Sergey Vyazovkin; Wolfgang Linert

Publisher
John Wiley and Sons
Year
1995
Tongue
English
Weight
460 KB
Volume
27
Category
Article
ISSN
0538-8066

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✦ Synopsis

A dependence of the activation energy upon the extent of conversion has been discovered for the thermal decomposition of C1q0CleL4 with piperidine (l), morpholine (2), and triphenylphosphine oxide (3) as the ligand (L). Within the interval of conversions 0-0.3 the process shows a decrease in the activation energy (230-130 (l), 130-50 (2), and 200-100 (3) kJ mol-l). The processes considered show an isokinetic relationship with Tiso = 255 2 15 K which corresponds to a vibrational frequency of visa = 177 2 10 cm-l. This value accords well with IR absorption bands assigned to the stretching vibration in the trigonal CuC13 chromophore as predicted by theory. Based on this, an assumption about the CuCl3-group as a central site of the reaction can be made. The IRand X-ray data are presented to support the assumption made. 0 1995

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