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Aluminium(III) porphyrin-carboxylate complexes, including a porphyrin pentamer, have been characterised by NMR spectroscopy, MALDI spectrometry and single crystal X-ray diffraction; these complexes can also be coordinated by a sixth, nitrogenous, ligand to the aluminium(III) centre.

Synthetic routes to a penta(4-pyridyl)cyclopentadienyl ligand are explored. The most successful route uses a palladium-catalysed pentapyridation of di(tert-butyl)phosphinoferrocene by using a procedure developed by Hartwig. The same method allows the synthesis of cyclopentadiene ligands substituted with 4-benzaldehydes or 4-phenylthiols. The pyridine ligands are formally five-connected nodes that may be linked by linear coordination metals to give closed spherical complexes of composition [(metal)(30)(ligand)(12)] as shown by molecular modelling. Experiment shows that the ligand complexes copper(I) and silver(I) with the expected 1:2.5 stoichiometry, and the (1)H NMR spectrum of the resulting product shows the ligands to be equivalent. NMR diffusion and light-scattering measurements support the formation of a species with a hydrodynamic radius of the order of 15 A, in agreement with the modelling studies. The resulting complex would be topologically identical to the C(60) fullerene structure.

A series of N₂O₂ tripodal tetradentate ligands derived from di-/tetra-tert-butyl substituted 2-[bis(2-hydroxybenzyl)aminomethyl]X (X = pyridine and benzimidazole) (H₂L(n) (n = 1-4)) and 8-[bis(3,5-di-tert-butyl-2-hydroxybenzyl)]aminoquinoline (H₂L⁵) were synthesised through a 4-step reaction scheme involving sequential formylation, reduction, bromination and alkylation. Treatment of H₂L(n) (n = 1-5) with [WO₂Cl₂(dme)] (dme = 1,2-dimethoxyethane) in the presence of triethylamine gave the corresponding cis-dioxotungsten(VI) complexes [WO₂(L(n))] (n = 1-5). The corresponding molybdenum analogues [MoO₂(L(n))] (n = 1-5) were also prepared from the reaction of [MoO₂(acac)₂] (acac = acetylacetonate) with H₂L(n) (n = 1-3) or [MoO₂Cl₂(dme)] (dme = 1,2-dimethoxyethane) with H₂L(n) (n = 4 and 5). All these compounds were fully characterised by a wide range of spectroscopic methods. The molecular structures of [MoO₂(L(n))] (n = 2, 4) and [WO₂(L²)] were also confirmed by single-crystal X-ray diffraction analysis. The catalytic activities of [MO₂(L(n))] (M = Mo, W; n = 1-4) towards epoxidation of styrene were also examined.