First Example of Cage PN-Macrocycle Copper Complexes with Intracavity Location of Unusual CuI Fragments.

In this study, 28-membered macrocyclic 1,5(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8(1,4)-tetrabenzenacyclooctaphane were synthesized by condensation of pyridinephosphine, paraformaldehyde, and primary diamines (bis(4-aminophenyl)methane or -sulfide. The first representatives of binuclear copper(I) complexes of P,N-containing cyclophanes with two 1,5-diaza-3,7-diphosphacyclooctane rings incorporated into a macrocyclic core and intracavity location of unusual, developed angle CuI moiety were obtained. The structure of one complex was established by X-ray diffraction analysis.

Dynamic Covalent Chemistry Approach toward 18-Membered PN Macrocycles and Their Nickel(II) Complexes.

A dynamic covalent chemistry approach was used for the stereoselective synthesis of 1,10-diaza-3,8,12,17-tetraphosphacyclooctadecanes via condensation reaction of 1,4-bis(organylphosphino)butane, formaldehyde, and primary amines. The obtained 18-membered PN macrocycles were isolated in pure form as - () or - (/) isomers. The structural features of the individual stereoisomers were revealed by NMR spectroscopy and X-ray structure analysis.

Synthesis and Structure of Iron (II) Complexes of Functionalized 1,5-Diaza-3,7-Diphosphacyclooctanes.

In order to synthesize new iron (II) complexes of 1,5-diaza-3,7-diphosphacyclooctanes with a wider variety of the substituents on ligands heteroatoms (including functionalized ones, namely, pyridyl groups) and co-ligands, it was found that these ligands with relatively small phenyl, benzyl, and pyridin-2-yl substituents on phosphorus atoms in acetonitrile formed bis-P,P-chelate -complexes [LFe(CHCN)] (BF), whereas P-mesityl-substituted ligand formed only monoligand P,P-complex [LFe(CHCN)] (BF). 3,7-dibenzyl-1,5-di(1'-()-phenylethyl)-1,5-diaza-3,7-diphosphacyclooctane reacted with hexahydrate of iron (II) tetrafluoroborate in acetone to give an unusual bis-ligand cationic complex of the composition [LFe(BF)] BF, where two fluorine atoms of the tetrafluoroborate unit occupied two pseudo-equatorial positions at roughly octahedral iron ion, according to X-ray diffraction data. 1,5-diaza-3,7-diphosphacyclooctanes replaced tetrahydrofurane and one of the carbonyl ligands of cyclopentadienyldicarbonyl(tetrahydrofuran)iron (II) tetrafluoroborate to form heteroligand complexes [CpFeL(CO)]BF.

The first representatives of tetranuclear gold(i) complexes of P,N-containing cyclophanes.

The first representatives of the tetranuclear gold(i) complexes of P,N-containing cyclophanes with two 1,5-diaza-3,7-diphosphacyclooctane rings incorporated into the macrocyclic core have been obtained. The complexation leads to a change in ligand conformations so that the diazadiphosphacyclooctane fragments of the complexes adopt twist-chair conformations, and two of the four gold(i) ions are located over and under the partially collapsed macrocyclic cavity. The complexes demonstrate moderate solid-state green emission.

Structure and dynamics of P,N-containing heterocycles and their metal complexes in solution.

Conformations and dynamics of 1,5-diaza-3,7-diphosphacyclooctane (1) with chiral l-menthyl substituents on the phosphorus atoms and several metal complexes thereof were investigated by a variety of DNMR methods. In solution 1 adopts a C(2) symmetrical "crown"-like conformation (CW) and the conformational preference and dynamics of the complexes depend on the type of metal: for the Cu complex the CW form is preferred, whereas the Pd, Pt, or Mo complexes exist in an equilibrium of two "chair-boat"-like conformations (CB/CB*). The barriers of interconversion between these two conformations for the Pd and Pt complexes are about 2 times higher than for the Mo complex.