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Nucleophilic substitution of an iron(ii) dichloroclathrochelate with diphenylphosphine sulfide under PTC afforded a monophosphorylated cage complex. This precursor undergoes further nucleophilic substitution with mono- and diamines giving P,N-substituted mono- and bis-clathrochelates; those with thiophosphoryl and pyridyl groups were used as N,S-donor macrobicyclic ligands toward the palladium(ii) ion. In the resulting Pd,Fe-binuclear 1 : 1 complexes, the clathrochelate moieties retain the geometry, characteristic of low-spin iron(ii) complexes, with a minor distortion caused by intramolecular interactions. The Pd(2+) ion has a twisted square-planar N2SCl-environment. The complexes thus obtained proved to be efficient catalysts of the Suzuki cross-coupling reaction.

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The 1,3-cycloaddition of ω-phosphoryl azides to activated internal alkynes such as dimethyl acetylenedicarboxylate and tetramethyl acetylenediphosphonate as well sodium azide to tetramethyl acetylenediphosphonate readily proceeds in water without any co-solvent or additive to afford the corresponding phosphorylated 1,2,3-triazoles in excellent yields. The ester group in carbalkoxy function of these compounds can be easily converted to carbamido group via the reaction with amines in MeOH thereby expanding the range of potentially biologically active heterocyclic aminophosphonates of such type.