The potential for stabilization of volatile flavourant molecules such as functionalized pyrazines by coordination to metal ions, and the application of the resultant coordination complexes as controlled release agents at elevated temperatures were explored. New complexes containing the flavourant molecules 2,3,5-trimethylpyrazine (TMP), 2-ethyl-3-methylpyrazine (EMP) and 2-acetylpyrazine (ACP) with copper(II) and copper(I) salts were prepared and structurally characterized. Representative examples of known copper(II) and calcium(II) complexes containing pyrazine carboxylic acids were also prepared. The complexes were examined by thermal analysis techniques and demonstrated, by a combination of thermogravimetric (TGA) and pyrolysis GC-MS analyses, to act as convenient reagents for the release of the parent pyrazine at elevated temperatures. Thus, pyrolysis GC-MS revealed that the complex [Cu3Cl3(EMP)2] n cleanly releases EMP in 96.5% selectivity at 200 °C. Of particular significance is that the calcium complex [Ca(3-aminopyrazine-2-carboxylate)2·H2O], under ramped pyrolysis conditions, was shown to undergo decarboxylation prior to the release of 2-aminopyrazine (AMP), as essentially the only volatile component, in the temperature range 600-800 °C. This finding provides a precedent for the application of complexes of pyrazinecarboxylate salts with metal ions (of which an almost infinite number of combinations is potentially available) as controlled release agents of the parent pyrazine molecule at elevated temperatures, suitable for exploitation by the foodstuffs, flavour and fragrance industries. Copyright © 2006 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]