title: Redox-active p-quinone-based Bis(pyrazol-1-yl)methane ligands: synthesis and coordination behaviour.
abstract: The synthesis, structural characterisation and coordination behaviour of mono- and ditopic p-hydroquinone-based bis(pyrazol-1-yl)methane ligands is described (i.e., 2-(pz2CH)C6H3(OH)2 (2a), 2-(pz2CH)-6-(tBu)C6H2(OH)2 (2b), 2-(pz2CH)-6-(tBu)C6H2(OSiiPr3)(OH) (2c), 2,5-(pz2CH)2C6H2(OH)2 (4)). Ligands 2a, 2b and 4 can be oxidised to their p-benzoquinone state on a preparative scale (2a ox, 2b ox, 4 ox). An octahedral Ni II complex [trans-Ni(2c)2] and square-planar Pd II complexes [Pd2bCl2] and [Pd2b ox Cl2] have been prepared. In the two Pd II species, the ligands are coordinated only through their pyrazolyl rings. The fact that [Pd2bC12] and [Pd2b oxC12] are isolable compounds proves that redox transitions involving the p-quinone substituent are fully reversible. In [Pd2b oxCl2], the methine proton is highly acidic and can be abstracted with bases as weak as NEt(3). The resulting anion dimerises to give a dinuclear macrocyclic Pd II complex, which has been structurally characterised. The methylated ligand 2-(pz2CMe)C6H3O2 (11 ox) and its Pd II complex [Pd11 oxCl2] are base-stable. A new class of redox-active ligands is now available with the potential for applications both in catalysis and in materials science.
authors.affiliation: Institut für Anorganische und Analytische Chemie, Johann Wolfgang Goethe-Universität Frankfurt am Main, Max-von-Laue-Strasse 7, 60438 Frankfurt, Germany.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Scheuermann
authors.forename: Tonia
authors.initials: T
authors.lastname: Kretz
authors.forename: Hannes
authors.initials: H
authors.lastname: Vitze
authors.forename: Jan W
authors.initials: JW
authors.lastname: Bats
authors.forename: Michael
authors.initials: M
authors.lastname: Bolte
authors.forename: Hans-Wolfram
authors.initials: HW
authors.lastname: Lerner
authors.forename: Matthias
authors.initials: M
authors.lastname: Wagner