An effective strategy of P,N-containing macrocycle design is described, which is based on covalent self-assembly processes in the course of Mannich-type condensations in three-component systems: primary phosphine (or secondary diphosphine)–formaldehyde–diamine with spatially divided functional groups (or primary amine). This approach allowed the authors to obtain various types of macrocyclic phosphines, namely cage cyclophanes with a 1,5-diaza-3,7-diphosphacyclooctane fragment in the basic framework, cyclophanes with linear P,N-containing spacers, P,N-containing corands and the first P,N-containing cryptand with four phosphine centers.

Amphiphilic 1,5‐diaza‐3,7‐diphosphacyclooctanes have been synthesized by condensation of hydrophobic primary arylphosphines, formaldehyde, and functionalized hydrophilic primary arylamines (5‐aminoisophthalic acid and the sodium salt of sulfanilic acid). These compounds readily form P,P‐chelate complexes with [PtCl₂(cod)], which are stable in water. The catalytic activity of palladium catalysts with 1,5‐diaza‐3,7‐diphosphacyclooctane ligands was studied in the copolymerization of ethylene and carbon monoxide. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:499–513, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20272

Novel macroheterocyclic tetraphosphines, namely, 1,1′,5,5′-bis(arylene)-bis(1,5-diaza-3,7-diphosphacyclooctanes) 2–6, were obtained without the use of high-dilution techniques or any matrix by the reaction of bis(hydroxymethyl)organylphosphines with primary aromatic diamines containing two p-phenylene fragments linked by various one-atom bridges in a molecular self-assembly process. The structures of 4, 5 and 6 were investigated by X-ray crystal structure analyses. The macrocyclic cavities can be described as a truncated rhombohedral prism with side faces formed by phenylene rings and 1,5-diaza-3,7-diphosphacyclooctanes in the truncated acute angles. In the crystals of these macrocycles, solvating DMF molecules are present, and a methyl group from each of two DMF molecules penetrates the macrocyclic cavities of 4 and 5 from either side, whereas only one disordered molecule of DMF penetrates the cavity of macrocycle 6. Different types of crystal packing are observed for the P-benzyl-substituted compounds 4 and 5 and for the P-mesityl-substituted compound 6: for 4 and 5 the formation of alternating layers containing the macrocycles and the DMF molecules is observed, in which the cavities of the macrocyclic molecules form channels and the DMF molecules are located in the centers of the channels; in the crystal of 6, six molecules are arranged around the axis in the fashion of a six-bladed propeller.