V. I. Maslennikova

Complexes of P(III)-phosphocavitands with Groups VI and VII transition metal carbonyls

Abstract A study has been made of the interaction between the new type of cavitands, P(III)-phosphocavitands, and the Cr, Mo, W, and Mn carbonyl complexes. The possibility has been shown for the directed coordination of all or some phosphorus atoms of the cavitand molecules with metals. The effect of the substituents at the phosphorus atoms in the macrocycles on the process selectivity has been revealed. The first metallocomplexes of phosphocavitands containing trivalent phosphorus atoms have been obtained.

AMIDOPHOSPHITES IN THE CHEMISTRY OF CALYX[4]RESORCINOLARENE

Abstract The possibility of using phosphorous amides for the phosphorylation of calyx[4]resorcinolarenes is found. This reaction can be directed to the synthesis of their octaphosphorylated derivatives or phosphocavitands. It is shown that the obtained compounds demonstrate substantially different properties depending on the character of their molecular matrix.

TETRAPROPYLPHOSPHOCAVITANDS: SYNTHESIS, STRUCTURE, AND PROPERTIES

Abstract Cyclophosphorylation of tetrapropylcalyxresorcin[4]arene by phosphorous amides gave P(III)-phosphocavitands, modification of which resulted in a series of P(V)-phosphocavitands with different substituents at phosphorus atoms. The first alkylation of amidophosphocavitands has been performed.

First heterobimetallic complexes of phosphocavitands

Abstract The synthesis and characterisation were described for tetranuclear phosphocavitand complexes 4 , where each phosphorus atom is coordinated to the silver atom, and tetranuclear heterobimetallic phosphocavitand complexes 6 , in which only three phosphorus atoms are coordinated to silver and the fourth phosphorus atom is coordinated to molybdenum. Compounds 4 were obtained by the reaction of AgBr with amidophosphitocavitands 1 . Compounds 6 were synthesised by the reaction of AgBr with mononuclear molybdenum complexes of amidophosphocavitands 3 . It was found that, in the presence of diethylammonium cation, 4a forms anionic complex [(C 2 H 5 ) 2 NH 2 ][cavitand·Ag 4 (μ-Br) 4 (μ 4 -Br)] ( 5 ), whose structure was supported by X-ray diffraction analysis.

Sterically oriented synthesis and structure of new perphosphorylated resorcinarenes

Tetraarylresorcinarenes in a chair conformation of C2h symmetry were synthesized by sterically oriented condensation of aromatic aldehydes with resorcinol and 2-methylresorcinol. By further phosphorylation of resorcinarenes with phosphorous amides perphosphorylated derivatives were obtained with rctt configuration of substituents at internuclear methylidene bridges. Structure of these compounds was proved using NMR spectroscopy and X-ray diffraction analysis.

Regioselective Synthesis and Structure of New Oligophosphorylated rctt Resorcinarenes

Abstract Regioselective phosphorylation of rctt tetranaphthyl resorcinarenes gave monofunctionalized derivatives with eight phosphamide groups immobilized on the macrocyclic matrix, as well as heterofunctionalized derivatives containing hydroxyl groups on the vertically oriented benzene rings and phosphorus fragments on the planar benzene rings. GRAPHICAL ABSTRACT

COMPLEXES OF PHOSPHOCAVITANDS WITH GROUP VI METALS

Abstract The first complexes of amidophosphito- and phosphitocavitands with the group VI transition metal hexacarbonyls have been obtained. It was shown that the liganding ability of P(III)-phosphocavitands depended on the nature of exocyclic substituents at the phosphorus atoms.

Synthesis of dinaphthylmethane derivatives containing carbamothioyloxy and carbamoylsulfanyl groups

Chemical modification of 1,1′-methylenedinaphthalen-2-ol and 1,1′-methylenedinaphthalen-2,7-diol, including thiocarbamoylation, Newman-Kwart rearrangement, and hydride reduction, afforded dinaphthylmethane derivatives containing carbamothioyloxy, carbamoylsulfanyl, and sulfanyl groups.

Pre-organized oligomodified resorcinarene ligands. Preparation, structure, and complex formation

Interaction of various conformations of resorcinarenes with carbamoyl chloride, thiocarbamoyl chloride, and trifluoromethanesulfonic acid anhydride has resulted in a series of derivatives with certain pre-organization of the macrocyclic scaffold and the immobilized electron-donating groups. Complex formation of the selected prepared compounds towards Pd(II) derivatives has been studied.

Cyclophosphorylation of polyphenols by diamidoarylphosphites

Abstract It was found that the cyclophosphorylation of polyphenols by diamidoarylphosphites proceeds via the rupture of only one P–N bond and one P–O bond, the second P–N bond remaining intact. It is supposed that the unusual lack of reactivity of the P–N bond is due to the spatial arrangement of the amido group with respect to the reaction site in phosphorylated intermediates 5 .