Synthesis of first representatives of 46-membered P,N,O-containing cyclophanes and their transition metal complexes

A condensation of phenyl- or l-menthylphosphine with formaldehyde and 4,4´-bis-(4´-aminophenoxy)biphenyl proceeding as a covalent self-assembly gave rise to the first representatives of 46-membered P,N,O-containing cyclophanes, namely, 13,17,83,87-tetra-R-3,6,10,13-tetraoxa-1,8(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,5,7,9,11,12,14(1,4)-octabenzenacyclotetradecaphanes (R = Ph (1), l-Ment (2)). The cage macrocyclic tetraphosphine 2 reacted with (cyclooctadiene)dichloroplatinum(ii) and -palladium(ii), as well as with (tetrahydrofuran)pentacarbonyltungsten(0) with the formation of binuclear complexes, in which the metal atoms are coordinated to 1,5-diaza-3,7-diphosphacyclooctane fragments by the P,P-chelate mode.