Metal- and ligand-directed one-pot syntheses, crystal structures, and properties of novel oxo-centered tetra- and hexametallic clusters

Saalfrank, Rolf W. and Reimann, Uwe and Goeritz, Mareike and Hampel, Frank and Scheurer, Andreas and Heinemann, Frank W. and Bueschel, Michael and Daub, Joerg and Schuenemann, Volker and Trautwein, Alfred X. (2002) Metal- and ligand-directed one-pot syntheses, crystal structures, and properties of novel oxo-centered tetra- and hexametallic clusters. CHEMISTRY-A EUROPEAN JOURNAL, 8 (16). pp. 3614-3619. ISSN 0947-65

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Abstract

Starting from closely related metal - ligand combinations, completely different oligomeric metal clusters are synthesized. Whereas, picoline-tetrazolylamide HL1 (1) and zinc or nickel acetate afforded [2 x 2] grids [M-4(L-1)(8)] (2), slightly different N-(2-methylthiazole-5-yl)-thiazole-2-carboxamide HL2 (5a) and nickel acetate yielded the monometallic complex [Ni(L-2)(2)(OH2)(2)] (6). In contrast, reaction of 5a with zinc acetate produced the tetrametallic zinc cluster [Zn4O(L-2)(4)(OAc)(2)] (7). Even more surprising, when 3-methyl-substituted HL3 (5b) instead of 2-methyl-substituted HL2 (5a) was allowed to react under identical conditions with zinc acetate, the cluster [Zn4O(L-3)(4)Cl-2] (8) crystallized from dichloromethane. Clusters 7 and 8 are isostructural. As for 7, in 8 two of the edges of the tetrahedron of zinc ions are doubly bridged, two are singly bridged, and the other two are nonbridged. On the other hand, when iron(II) acetate under aerobic conditions was allowed to react with 5a, the unprecedented complex [{Fe3O(L-2)(2)-(OAC)(4)}(2)O] (9) was isolated. Cluster 9 is composed of two trimetallic, triangular mu(3)-O2--centered [Fe3O(L-2)(2)(OAC)(4)](+) modules, linked by an almost linear mu(2)-O2- bridge. The Mossbauer spectrum together with cyclic voltammetric and square-wave voltammetric measurements of 9 are reported, and 6-9 were characterized unequivocally by single-crystal X-ray structure analyses.

Item Type: Article
Uncontrolled Keywords: HEXANUCLEAR FERRIC COMPLEX; 5 GROUND-STATE; TRANSITION-METALS; SPIN FRUSTRATION; ACID COMPLEXES; SUPERMOLECULES; CONSTRUCTION; CHEMISTRY; MOLECULES; UNITS; cluster compounds; cyclic voltammetry; Mossbauer spectroscopy; N ligands; self-assembly; supramolecular chemistry
Subjects: 500 Science > 540 Chemistry & allied sciences
Divisions: Chemistry and Pharmacy > Institut für Organische Chemie > Alumni or Retired Professors > Prof. Dr. Jörg Daub
Depositing User: Dr. Gernot Deinzer
Date Deposited: 02 Sep 2021 08:11
Last Modified: 02 Sep 2021 08:11
URI: https://pred.uni-regensburg.de/id/eprint/39977

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