E. I. Sinyavskaya

Reaction of alkali-metal 2,4-dinitrophenolates with 1,4,7,10-tetra(diphenylphosphinylethyl)-1,4,7,10-tetraazacyclododecane

Conclusions1.A new electroneutral cyclopendant organophosphorus ligand, 1,4,7,10-tetra(diphenyl-phosphinylethyl)-1, 4,7,10-tetraazacyclododecane, was synthesized.2.The reaction of this ligand with alkali-metal 2,4-dinitrophenolates in a THF-CHCl3 mixture was studied, and stability constants of Li, Na, K and Cs complexes with composition of [ML+] were determined.3.From comparison with other ligands, an assumption was made on the coordination of the metal ions in complexes by endocyclic N atoms of the amino groups and O atoms of the exocyclic phosphoryl groups.

Complexes of alkali metals, magnesium, and calcium with phosphoryl-containing pendant tetraazamacrocyclic ligands

Conclusions1.The reaction of lithium, sodium, potassium, and cesium 2,4-dinitrophenoxides and magnesium and calcium iodides with a number of phosphoryl-containing pendant tetraazamacrocyclic ligands L in nonaqueous solvents was studied.2.The stability constants of complexes of alkali metals with the composition [ML]+ and of magnesium and calcium with the composition [MLI]+ with the indicated ligands were determined.3.Among the investigated macrocyclic compounds, the ligand that contains a 14-membered macroring and an ethylene bridge in the side chain is the most effective complexing agent.

Coordination compounds of alkali metals and copper with cambamoyl phosphine oxide derivatives

Conclusions1.Stability constants for alkali metal complexes of composition [ML]+ and a copper complex [CuLCl]+, which are formed via treatment of alkali metal 2,4-dinitrophenolate or copper chloride with a series of carbamoyl phosphine oxide derivatives, have been determined in anhydrous solutions.2.The most stable complexes are formed by ligands containing an aryl substituent attached to the phosphorus atom.

Nature of the complexes formed by alkali metal halides with phosphine oxides

Reaction of alkali metal halides (MX) with methylenediphosphine oxides and various related compounds in nonaqueous solutions leads to the formation of complex compounds. The compositions, properties, and stabilities of these compounds, which have been studied in detail in acetonitrile, are determined by the nature of the cations and anions of the alkali metal halides. Formation of neutral complexes with the composition [MX · L] and cationic complexes with the composition [ML]+ has been established. The most characteristic representative of complexes of the first type is [NaI · L]; in the complexes studied, L=R2P(O)CH2P(O)R2 (R=Bu, BuO, or Ph), Ph2P(O)CH2P(O) (OC2H5)CH2P(O)Ph2 and (p-OCH3C6H4)2P(O)CH2P(O)(C6H4CF3-p)2. Compound [LiL]+ is characteristic of complexes of the second type; the compounds containing Ph3P(O), Ph2P(O)CH2P(O)Ph2, and Ph2P(O)CH2P(O)(OC2H5)CH2P(O)Ph2 as ligands have been studied. Stability constants of the complexes [NaI · L] and [LiL]+ have been determined by measuring the dependence of the electrical conductivity of solutions of the alkali metal halides in acetonitrile on the concentration of the ligands. The complex-forming power of phosphine oxides increases with increase in the number of P=O groups. Stabilities of the complexes [NaI · L] with ligands with identical structure decrease with increase in the electronegativity of the substituents on the phosphorus atoms.