Syntheses and characterization of mixed acetylacetonate-catecholate complexes of zirconium, [Zr3(acac)4(cat)4(MeOH)2], [Zr(acac)2(DBcat)]2 (H2DBcat=3,5-di-tert-butylcatechol) and [Zr4(μ4-O)(acac)4(DBcat)3(OMe)4(MeOH)]

Reactions of the acetylacetonate complex [Zr(acac)(4)] with catechols have been investigated. Two crystalline complexes [Zr-3(acac)(4)(cat)(4)(MeOH)(2)] 1 and [Zr(acac)(2)(DBcat)](2) 2 (H(2)DBcat=3,5-di-tert-butylcatechol) are isolated from the respective reactions in toluene, and their solid-state structures established by X-ray diffraction studies. Complex 2 consists of an edge-shared capped trigonal prismatic structure involving two symmetry related [Zr(acac)(2)(DBcat)] units, while 1 is best visualized as a Zr-3 complex, possessing two [Zr(acac)(2)(cat)(MeOH)] units linked to the central [Zr(cat)(2)] fragment via four bridging catecholate ligands. Their reactivity was investigated; treatment of 2 with a trace amount of water in a solution of methanol and CH2Cl2 gave a Zr-4 oxo complex [Zr-4(mu(4)-O)(acac)(4)(DBcat)(3)(OMe)(4)(MeOH)] 3.