The dismutation ofarylene phosphorodiamidites derived from the simplest phenols and naphthols and of their dibasic analogs was studied. The main regular trends of this process and the limits of its synthetic applicability were determined.

The complex formation of TiF 4 with the phosphorylated ketone Ph 2 P(O)CH(Me)CH 2 C(O)Et (L), containing an asymmetric carbon atom in the aliphatic hydrocarbon group and representing a racemic mixture of enantiomers, was studied by 19 F{ 1 H} and 31 P{ 1 H} NMR spectroscopy. The composition of complexes formed in the solution was determined; analysis of the 19 F NMR spectra resorting to the heterotropicity concept was used to assign the resonance lines to two chiral optically active racemic and meso- stereoisomers of cis -TiF 4 L 2 . The configurations of enantiomers of the monodentate ligand coexisting in the coordination sphere were found to have a crucial effect on the axial fluorine atoms of mixed octahedral cis -tetrafluoro d 0 transition metal complexes. A new efficient method was developed for the synthesis of ligand L.

Some peculiarities of the effect of enantiomers of the monodentate ligand on the stereoisomerism of the mixed octahedral tetrafluoride complexes of d0-transition metals are established by the 19F{1Н} and 31Р{1Н} NMR methods for the complex formation of TiF4 with Ph2P(O)CH2CH(OH)Me (L) having the asymmetric carbon atom in the aliphatic hydrocarbon radical and being a racemic mixture of enantiomers in СН2Сl2. The compositions of the complexes formed in solutions are determined. The conclusion about the relative stereochemical configuration of the chiral and meso-stereoisomers of the geometric isomers of the TiF4L2 octahedral complex is based on an analysis of the 19F NMR spectra using the heterotropic concept.

The reaction of TiF4 with PhP(O)[CH2C(O)NMe2]2 in CH2Cl2 has been studied by 19F NMR spectroscopy. It has been found that the major reaction products are chelate tetrafluoro complex (η2-L)TiF4 where the ligand is coordinated to the titanium ion through the P=O and C=O groups and cis-TiF4(ОР···L)2 where both ligands are coordinated to the central ion through the more basic P=O groups. Spectral features of the tetrafluoro chelate have been studied, which have been attributed for the first time to the appearance of a chiral center at chelate coordination. The character of manifestation of conformational isomerism of the chelate ring and chiral center in the chelating ligand in mixed octahedral complexes of d0 transition metal fluorides in 19F NMR spectra is discussed.

The compositions and structures of the products of the reaction of TaF 5 with Ph 2 P(O)(CH 2 ) 2 C(O)NМе 2 (L) in СН 3 СN and СН 2 Сl 2 are studied by the 19 F and 31 Р NMR methods. As the hydrocarbon bridge between the Р=О and С=О donor groups in carbamoylphosphine oxides elongates from –СН 2 – to (–СН 2 –) 2 , the chelation ability of the ligand is retained and the composition of the complexes formed in a solution is determined by the ratio of components. The compositions and structures of the hydrolysis products are studied. Distinctions in the coordination behavior of the considered ligand during complex formation with tantalum pentafluoride and titanium tetrafluoride are studied.

Reactions of catechin and dihydroquercetin flavonoids with amino acids containing primary amino groups have been conducted. Amino acids can be used in both electrophilic substitution (Mannich aminomethylation) and electrophilic substitution (acylation) reactions.

Effect of enantiomers of a monodentate ligand on the stereoisomerism of mixed octahedral cis-tetrafluoro complexes of d0 transition metals has been studied by 19F{1H} and 31P{1H} NMR by the example of TiF4 complexation in CH2Cl2 with Ph2P(O)CH2CH(OH)Me (L) containing asymmetric carbon atom in the aliphatic hydrocarbon group that constitutes a racemic mixture of enantiomers. Composition of complexes formed in solution has been determined, conclusion has been drawn on the relative stereochemical configuration of the chiral and meso stereoisomers of octahedral complex cis-TiF4L2 on the basis of analysis of 19F NMR spectra, using the heterotropism concept.

The compositions and structures of the products of the reaction of TaF5 with Ph2P(O)(CH2)2C(O)NМе2 (L) in СН3СN and СН2Сl2 are studied by the 19F and 31Р NMR methods. As the hydrocarbon bridge between the Р=О and С=О donor groups in carbamoylphosphine oxides elongates from –СН2– to (–СН2–)2, the chelation ability of the ligand is retained and the composition of the complexes formed in a solution is determined by the ratio of components. The compositions and structures of the hydrolysis products are studied. Distinctions in the coordination behavior of the considered ligand during complex formation with tantalum pentafluoride and titanium tetrafluoride are studied.

The reaction of methyl- and phenyldichlorophosphonates with phenols in the presence of anhydrous magnesium chloride (catalyst) or magnesium metal (procatalyst) has been used as a simple, efficient, and industrially feasible method for the synthesis of the corresponding O-aryl alkyl(aryl)phosphonochloridates.

The composition and structure of the products of the reaction of titanium tetrafluoride with Ph2P(O)(CH2)2C(O)NМе2 (L), the simplest representative of diphenyl[2-(N,N-dialkylcarbamoyl)ethyl]phosphine oxides, in a СН2Сl2 have been studied by 19F and 31P NMR. It has been shown for the first time that functionalized phosphine oxides form stable seven-membered chelate heterocycles on complexes of d° transition metals. On the basis of NMR data, previously unknown conformational isomerism of the seven-membered TiOPCCCO heterocycle in solution has been proposed. A simple and rather efficient method of synthesis of the ligand (L) from commercially available reagents has been developed.

The products resulting from the reaction of TiF4 with Ph2P(O)(CH2)2C(O)Me (L') in CH2Cl2 have been studied by 19F{1H} and 31P{1H} NMR spectroscopy. At a twofold excess of L', solution contains cis-TiF4(L')2 (>90%), trans-TiF4(L')2, and fac-[TiF3L3']+, where L' is coordinated via the P=O group, as well as the dimer [(Ti2F7L'2)2]+, where L' is coordinated through the P=O and C=O groups. An equimolar solution contains dimeric and polynuclear complexes containing moieties with three terminal cis fluorine ions, while the other coordination sites are occupied by the P=O groups and F– bridges. At a twofold excess of TiF4, ligand L' coordinates via the P=O and C=O groups and behaves as a bridge along with F– ions. Thermodynamic stability of the structures of the TiF4L'2 isomers and the structure of [(µ-F)(µ-L')2(TiF3)2]+ has been calculated.