title: Sterically-directed consecutive and size-selective self-assembly of palladium diphosphane complexes with an Ar-BIAN ligand: unexpected formation of pentameric and hexameric aggregates.
abstract: The coordination properties of N,N'-bis[4-(4-pyridyl)phenyl]acenaphthenequinonediimine (L(1)) and N,N'-bis[4-(2-pyridyl)phenyl]acenaphthenequinonediimine (L(2)) were investigated in self-assembly with palladium diphosphane complexes [Pd(P;P)(H(2)O)(2)](OTf)(2) (OTf = triflate) by using various analytical techniques, including multinuclear ((1)H, (15)N, and (31)P) NMR spectroscopy and mass spectrometry (P;P = dppp, dppf, dppe; dppp = bis(diphenylphosphanyl)propane, dppf = bis(diphenylphosphanyl)ferrocene, and dppe = bis(diphenylphosphanyl)ethane). Beside the expected trimeric and tetrameric species, the interaction of an equimolar mixture of [Pd(dppp)](2+) ions and L(1) also generates pentameric aggregates. Due to the E/Z isomerism of L(1), a dimeric product was also observed. In all of these species, which correspond to the general formula [Pd(dppp)L(1)](n)(OTf)(2n) (n = 2-5), the L(1) ligand is coordinated to the Pd center only through the terminal pyridyl groups. Introduction of a second equivalent of the [Pd(dppp)](2+) tecton results in coordination to the internal, sterically more encumbered chelating site and induces enhancement of the higher nuclearity components. The presence of higher-order aggregates (n = 5, 6), which were unexpected for the interaction of cis-protected palladium corners with linear ditopic bridging ligands, has been demonstrated both by mass-spectrometric and DOSY NMR spectroscopic analysis. The sequential coordination of the [Pd(dppp)](2+) ion is attributed to the dissimilar steric properties of the two coordination sites. In the self-assembled species formed in a 1:1:1 mixture of [Pd(dppp)](2+)/[Pd(dppe)](2+)/L(1), the sterically more demanding [Pd(dppp)](2+) tectons are attached selectively to the pyridyl groups, whereas the more hindered imino nitrogen atoms coordinate the less bulky dppe complexes, thus resulting in a sterically directed, size-selective sorting of the metal tectons. The propensity of the new ligands to incorporate hydrogen-bonded solvent molecules at the chelating site was confirmed by X-ray diffraction studies.
authors.affiliation: Chemical Research Center, Hungarian Academy of Sciences, 1525 Budapest, POB 17, Hungary.
authors.forename: Eszter
authors.initials: E
authors.lastname: Holló-Sitkei
authors.forename: Gábor
authors.initials: G
authors.lastname: Szalontai
authors.forename: Isabella
authors.initials: I
authors.lastname: Lois
authors.forename: Agnes
authors.initials: A
authors.lastname: Gömöry
authors.forename: Ferenc
authors.initials: F
authors.lastname: Pollreisz
authors.forename: László
authors.initials: L
authors.lastname: Párkányi
authors.forename: Hershel
authors.initials: H
authors.lastname: Jude
authors.forename: Gábor
authors.initials: G
authors.lastname: Besenyei