Metal chelation aptitudes of bis(o-azaheteroaryl)methanes as tuned by heterocycle charge demands

Alessandro Abbotto, Silvia Bradamante, Antonio Facchetti, Giorgio A. Pagani*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

58 Scopus citations


We describe the synthesis of a number of 1,3-azol-2-yl-, 1,3-benzazol-2-yl-, and azinyl-based bis- (o-azaheteroaryl)methanes (LH, L- = Het2CH-) and their coordinating properties toward divalent transition metals (Zn, Cu, Co, Ni, Hg, Pd). This extended investigation includes both symmetrical and unsymmetrical ligands based on several substituted and/or unsubstituted thiazole, benzothiazole, benzoxazole, benzimidazole, pyridine, and quinoline derivatives. Depending on the structure and electron properties of the ligand, a vast set of neutral chelates ML2 were obtained, where the ligand is present in its carbanionic form L-. Additionally, we have prepared salt complexes [M(LH)n]-Xm, where the ligand is present as a neutral system. Neutral chelates were typically obtained by the reaction of the ligand with metal acetates in alcoholic solution; salt complexes were formed by reaction with other metal salts such as chlorides. By exploring the coordinating properties of several bisheteroarylmethane ligands based on heteroaromatics of variable π-electron structure and substitution pattern, we demonstrate that the formation of neutral chelates is strictly dependent on the electron-withdrawing capacity (charge demand) of the heteroaromatic moiety. The latter primarily dictates the efficiency by which the negative charge of the anionic ligand L- is stabilized by delocalization in ML2 and, therefore, the stability of the chelate itself. On the basis of the large number and the variable nature of the nitrogen ligands used, we confirm the general validity of the charge-demand-dependent formation of chelates. This key factor can therefore be used for the efficient design of new π-deficient heteroaromatic nitrogen ligands in chelates of great potential in many synthetic, catalytic, and technological fields.

Original languageEnglish (US)
Pages (from-to)5753-5772
Number of pages20
JournalJournal of Organic Chemistry
Issue number16
StatePublished - Aug 9 2002

ASJC Scopus subject areas

  • Organic Chemistry


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