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 3 axis in the fashion of a six-bladed propeller.

The highly effective self-assembly process between 2,4,6-tris(isopropyl)phenylphosphine or mesitylphosphine, formaldehyde and 1,4-bis(alpha-(4'-aminophenyl)isopropyl)benzene results in the formation of a novel type of heterocyclophane which is able to encapsulate organic molecules as well as being a potential ligand for transition metals inside the intramolecular cavity. Compounds of this type can be regarded as potential precursors for a new kind of molecular reactors.

A dimer of thioxo-N-t-butylimino(trimethy1siloxy)-phosphorane 5 has been prepared by reaction of tris(trimethylsily1)phosphine with N-sulfiny1-Ntert-butylamine. The structure of 5 has been confirmed by X-ray analysis data. l-Aza-2-thia-3-phosphaallene 1, thiaphosphaziridine 3, iminophosphine P-sulfide 4 are postulated as intermediates of the reaction studied.

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The effective self-assembly process between phenylphosphine, formaldehyde and racemic N-alkyl-2,6-diamino-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximides

tert-Butylaminophosphaalkyne 4 is shown to dimerize in alkaline medium to I -tert-butyl-3-tert-butylamino-l,2,4-azadiphosphole 1-the first representative of I ,2,4-azadiphospholes. The structure of 1 has been determined by IR and 31P NMR spectroscopy and by X-ray crystallography. Compound 1 crystallizes in the triclinic space group Pi with a = 10.356(7), b = I I .817(5), c = 11.830(3) A, a = 88.51(3), p = 78.61(4), y = 77.05(4)", V = 1383(1) A3, Z = 4 (two independent molecules).

Condensation of bis(hydroxymethyl)mesityl and bis(hydroxymethyl)phenylphosphines with N,N´ disubstituted bis(4 aminophenyl)methanes and bis(4 amino 3 carboxy phenyl)methane occurred as covalent self assembly spontaneously giving a mixture of trans and cis diastereomers of 1,5,19,23 tetra R´ 3,21 di R 1,5,19,23 tetraaza 3,21 diphospha[5.1.5.1]paracyclophanes as the major products. The trans isomer (R is mesityl; R´ is methyl) was isolated in the individual state and structurally characterized by X ray diffraction analysis. Sulfurization of macrocyclic diphosphines (R = Ph; R´ is 3 pyridylmethyl or 4 pyri dylmethyl) gave the corresponding diphosphine disulfides, the trans stereoisomer being iso lated in the individual state.Macrocycles containing soft electron donating sites (in particular, tricoordinate phosphorus atoms) are of con stant interest primarily as a basis for development of cata lytic systems with reactive sites inside or adjacent to the macrocyclic cavity. 1,2 In such macrocycles, secondary in teractions of the cavity with substrates and reagents be come possible, thus making catalytic processes more effi cient and selective. Specific catalytic properties have been discovered with both macrocycles containing phosphine sites at the periphery of the cavity (such as phosphino cyclodextrins, 3,4 phosphinocalixarenes, 5 and cyclophanes with exocyclic phosphino groups (e.g., PhanePhos 6 ) and compounds with P atoms in the macrocycle itself. 1,2 In addition, phosphorus containing macrocycles are of in terest for design of supramolecular systems: receptors and sensors with specific properties. 7,8 From either point of view, cyclophanes with tricoordinate phosphorus atoms in the macrocycles composed of aromatic building blocks (e.g., m and p arylene fragments capable of forming deep hydrophobic cavities) are attractive. However, despite a great number of known P containing macrocycles, de scribed 9-11 cyclophanes of this type are relatively few, mostly including macrocyclic diphosphites, diphospho nites, and bis(phosphoramidites). 11-16 Recently, we have developed an efficient approach to the synthesis of cage type cyclophanes containing four phosphine sites, namely, 1,5(1,5) di(1,5 diaza 3,7 diphosphacyclo octana) 2,4,6,8(1,4) tetrabenzenacyclooctaphanes. The approach involves condensation of bis(hydroxymethyl)or ganylphosphines with primary diamines containing spac ers formed by two p phenylene fragments linked by vari ous monoatomic bridges. 17,18 At high concentrations of the reagents and in the absence of templates, those reac tions mainly yielded macrocycles via covalent self as sembly. 18 The goal of the present work was to further develop this approach and use it for the synthesis of more flexible cyclophanes with two tricoordinate P atoms in the macrocycle. To solve this problem, here we studied reactions of bis(hydroxymethyl)phenyl and bis(hydroxymethyl)mesitylphosphines with a number of secondary diamines containing di(p phenylene)me thane spacers: bis(4 methylaminophenyl)methane 1 (see Ref. 19), bi...