N Donor substituted acetylacetones – versatile ditopic ligands

Abstract

Abstract Acetylacetone (2,4-pentanedione) derivatives with N donor substituents represent ditopic ligands with coordination sites of distinctly different Pearson hardness. Deprotonation of the acetylacetone (Hacac) moiety leads to O,O′ chelating monoanionic (acac) ligands suitable for coordination to hard cations. The softer N donor site(s) preferably act as nucleophiles towards softer partners. When the organic molecules are employed as linkers and coordinate via either site, they are often selective and allow to synthesize well-ordered heterometallic solids. This review addresses the derivatives of 17 pentanediones with nitrile, pyridyl and pyrazolyl moieties as N donor substituents, with an emphasis on structurally characterized compounds. Depending on the N donor substituents and the cations, O,O′ or N coordination will dominate. The nitrile-substituted compounds essentially behave as acetylacetones; they may easily O,O′ coordinate to a wide range of cations whereas N coordination is limited to AgI, CuI or, in the case of less soft cations, to longer and presumably weaker contacts, e.g. to the more distant sites in Jahn–Teller distorted CuII. In contrast, pyridyl-substituted pentanediones act as N donor ligands, regardless whether their (H)acac site is chelating a cation or not. The still scarcely explored pyrazolyl derivative shows the most complex coordination pattern: it may be deprotonated both at the acetylacetone and the pyrazol site, the latter affording N,N′ bridging ligands. In addition to N donor nucleophilicity, the distance between the alternative coordination sites and their mutual orientation are relevant for crystal engineering applications.