Certi Mazza M T, De Cicco L, De Rosa G, De Rosa R, Caramazza R
Dipartimento di Chimica Farmaceutica e Tossicologica, Università di Napoli Federico II.
Boll Soc Ital Biol Sper. 1996 Mar-Apr;72(3-4):79-86.
The study on the co-ordination chemistry of the complexes with thiolic heterocyclic ligands is based on the ion metals binding precisely to the sulphur atom. Studies were consequently carried out on the complexes with some thiolic ligands, such as: 2-imidazolidine-thione (IMT), hydantoin (ID), 2-thiohydantoin (TIOID), rhodanine (RD), 2-mercaptoimidazole (MI), 2-mercapto-1-methylimidazole (MMI) and 2-mercaptopyridine (MPYR), supposing that the co-ordination bond between sulphur and metal is stronger than the possible bond between nitrogen or oxygen and metal due to the minor difference in electronegativity existing between sulphur and metal compared with that existing between nitrogen or oxygen and metal. Complexes of the kind we prepared generally present relatively low constants of instability, marking a strong bond between the metal and the ligand. This would seem to be in direct correlation with the anti-bacterial and herbicidal activity. The activity of the complex in fact proves to be more marked than that of the pure ligand, and the increase appears to be in proportion to the strength of the bond between the metal and the ligand, as seen by the low values of the relative constants of instability. We may imagine that the decrease in the constants of instability corresponds to an increase in the strength of the co-ordination bond and to a parallel increase in the activity and the hypothesis is in accordance with the premised correlation between the strength of the metal-ligand bond and the biological activity.
关于含硫杂环配体配合物的配位化学研究是基于离子金属与硫原子的精确结合。因此,对一些含硫配体的配合物进行了研究,这些配体包括:2-咪唑烷硫酮(IMT)、乙内酰脲(ID)、2-硫代乙内酰脲(TIOID)、若丹宁(RD)、2-巯基咪唑(MI)、2-巯基-1-甲基咪唑(MMI)和2-巯基吡啶(MPYR),假定硫与金属之间的配位键比氮或氧与金属之间可能形成的键更强,这是因为硫与金属之间的电负性差异比氮或氧与金属之间的电负性差异小。我们制备的这类配合物通常具有相对较低的不稳定常数,这表明金属与配体之间形成了强键。这似乎与抗菌和除草活性直接相关。事实上,配合物的活性比纯配体的活性更显著,而且这种增加似乎与金属和配体之间键的强度成正比,这从相对不稳定常数的低值可以看出。我们可以想象,不稳定常数的降低对应于配位键强度的增加以及活性的相应增加,并且这一假设与金属 - 配体键强度和生物活性之间的前提相关性是一致的。