The alternative coordination
sites of 3-(3,5-dimethyl-pyrazol-4-yl)pentane-2,4-dione
(H2acacPz) differ with respect to Pearson hardness. The
softer, heterocyclic moiety was used as N donor toward Zn(II) and
Ag(I); it yielded a tetrahedral, neutral Zn complex in the former
and a monocationic, linear bis(ligand) Ag complex in the latter case.
After deprotonation with silver benzoate, the pyrazolyl ring may act
as a monoanionic N,N′-bridge
between neighboring cations in a hexanuclear Ag aggregate; in addition
to ligand-supported Ag···Ag distances of ca. 3.2 Å,
these aggregates feature ligand-unsupported argentophilic interactions
of ca. 2.9 Å. With stronger bases and in the presence of oxophilic
Mg cations, the harder hydroxyketone part of the H2acacPz
ligand may be deprotonated to a chelating acetylacetonate. The resulting
bis(ligand) Mg complex has been used as starting compound for a bimetallic
derivative: the ditopic ligand allows coordinating cadmium acetate
to its dangling N donor site, thus, bridging divalent Mg and Cd in
a bimetallic three-dimensional coordination network of pts topology.