Acid/base responsive assembly/dis-assembly of a family of zirconium(IV) clusters with a cyclic imide-dioxime ligand

• Published in: Dalton transactions : an international journal of inorganic chemistry 2022-02, Vol.51 (5), p.1806-1818
• Main Authors: Passadis, Stamatis S, Hadjithoma, Sofia, Papanikolaou, Michael G, Keramidas, Anastasios D, Miras, Haralampos N, Kabanos, Themistoklis A
• Format: Article
• Language: English
• Subjects: Aqueous solutions; Assembly; Cemented carbides; Clusters; Crystal structure; Ions; Ligands; Mass spectrometry; NMR spectroscopy; Oxidation; Piperidine; Scientific imaging; Sequestering; Single crystals; Structural analysis; Structural stability; Tetrahedra; Titanium; Water chemistry; Zirconium
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d1dt03641f

The hydrolytically stable dioxime ligand (2 -6 )-piperidine-2,6-dione (H pidiox) acts as a strong chelator mainly with hard metals in high oxidation states, a pre-requisite for potential applications in metal sequestering processes from aqueous solutions. Reaction of ZrCl with H pidiox in methanol gives the mononuclear compound [Zr (η ,η ,η -H pidiox- , , ') (OH ) ]Cl ·H O·CH OH (1), while the same reaction mixture in the presence of KOH gave the pentanuclear ZrOC [ZrIV5(μ -OH) (OH ) (μ -η ,η ,η -Hpidiox- , , ') (η ,η ,η -Hpidiox , , ') ]·5KCl·3CH OH·8H O (2). Compound 1 is formed at very acidic pH = 0, and the pentanuclear ZrOC 2 at higher pH values (pH = 2). Compounds 1 and 2 were characterized by single crystal X-ray structure analysis, multi-nuclear NMR spectroscopy and ESI-MS spectrometry. The single crystal X-ray structure analysis of 1 revealed a mononuclear zirconium(IV) compound containing an eight-coordinate zirconium atom bound to two singly deprotonated H pidiox ligands and two water molecules in a severely distorted bicapped octahedral geometry. The pentanuclear ZrOC 2 constitutes the second example of a Zr cluster to be reported and the first one in which the four zirconium atoms are arranged in a tetrahedral arrangement with the fifth occupying the center of the tetrahedron. 1D and 2D NMR spectroscopies of the acidic CD OD solutions of complex 1 reveal a fast equilibrium between 1 and 2. Addition of KOH into a CH OH solution of 2 results in the controlled fast transformation of 2 to an asymmetric hexanuclear ZrOC 3 as evidenced by the NMR and real-time ESI-MS solution studies. Further addition of KOH to the solution of 3 leads to the ZrOC 4, and on the basis of NMR and ESI-MS data and in comparison with the known hexanuclear titanium(IV)/H pidiox cluster, it is concluded that the cluster 4 should have a hexanuclear structure. Electrospray ionization mass spectrometry (ESI-MS) demonstrated not only the structural stability 1 and 2 in solution, but also revealed the reversible pH driven dis-assembly/re-assembly process between the monomeric 1 and the pentanuclear ZrOC 2.