I. S. Ivanova

Synthesis, vibrational spectra, and crystal and molecular structure of 1,5-bis[2-(dihydroxyphosphinyl)phenoxy]-3-oxapentane dihydrate [(HO)2(O)P(C6H4)(OCH2CH2)2O(C6H4)P(O)(OH)2(H2O)] · H2O

A modified method of synthesis of a phosphoryl podand, 1,5-bis[2-(dihydroxyphosphinyl)phenoxy]-3-oxapentane (L), has been developed. The IR spectra of this podand and its dehydrate (L [L · H2O] · H2O (I) have been studied, the structure of I has been determined by X-ray crystallography. The crystals are orthorhombic, a = 9.4006(19) Å, b = 25.494(5) Å, c = 8.4264(17) Å, V = 2019.5(7) Å3, Z = 4, space group Pna21, R = 0.0512 for 3016 reflections with I > 2σ(I). Compound I is a host-guest molecular complex. Phosphoryl podand L acts as a host molecule, and one of the water molecules (H2O(11)) is a guest. This molecule forms one donor and one acceptor intramolecular hydrogen bond with hydroxyl groups of two phosphoryl groups (O(8)H(4) and O(3)H(2)) and combines them into an 18-membered macrocyclic ring, acting as a kind of “lock.” The H2O(11) molecule forms a second donor intramolecular hydrogen bond with the O(5) ether atom. The neutral molecular complexes are linked by hydrogen bonds directly and through the second water molecule (H2O(10)) into chains running along the c axis.

Synthesis of 2-(diphenylphosphoryl)phenyl ethers of ethylene glycols and structure of their sodium and potassium complexes

Phase-transfer catalysis and template assembly on sodium and cesium cations were used to prepare 2-(diphenylphosphoryl)phenyl ethers of ethylene glycols Ln with varied number of polyether units (n = 3–8). Previously unknown dinitro and disulfo derivatives of 2-(diphenylphosphoryl)phenyl ethers of di- and triethylene glycols were synthesized. Complexes [NaL4]NCS·C6H6, [NaL4]ClO4, [KL5]NCS, and [KL5]ReO4 were synthesized, and their crystal structure was studied. Structure–stability constant correlations were found for alkali metal complexes with phosphoryl podands Ln and isodentate crown ethers.

Neodymium, erbium, and europium complexes with 1,6-bis(diphenylphosphoryl)-2,5-dioxahexane (L): The crystal structure of [Nd2(NO3)6L3]

Solid complexes M(NO3)3 · 1.5L (M = Nd, Er, Eu; L is 1,6-bis(diphenylphosphoryl)-2,5-dioxahexane) have been synthesized. A new, convenient method of synthesis of L has been suggested. The crystal structure of [Nd2(NO3)6L3] has been determined by single-crystal X-ray diffraction. The nonacoordination environments of the Nd(1) and Nd(2) atoms are composed each of six O atoms of bidentate nitrate ions and three phosphoryl O atoms of the L molecules (av. Nd-O, 2.543 and 2.374 Å, respectively). Two independent L molecules act as bridges linking the Nd atoms to form centrosymmetric tetramers [L-Nd(NO3)3-L-Nd(NO3)3-L2-Nd(NO3)3-L-Nd(NO3)3L]. The third L molecule is disordered over two positions with site occupancy factors of 0.602(4) and 0.398(4) so that most of the molecules chelate the terminal Nd atoms in the tetramer, and the other molecules combine tetramers into longer associates. On the basis of elemental analysis data and IR spectra, it has been assumed that the Er and Eu complexes have the same structure as [Nd2(NO3)6L3].

Modified methods to synthesize of 1,8-bis[2-(diphenylphosphoryl)phenoxy]-3,6-dioxaoctane (L). Crystal structure and vibration spectra of [LiL]ClO4·2C6H6

Modified methods to synthesize, 1,8-bis[2-diphenylphosphoryl)phenoxy]-3,6-dioxaoctane phosphoryl podand (L), an effective complexing agent for the lithium cation, is reported. The possibility to use the phase-transfer catalysis and microwave irradiation is shown. The crystal structure of coordination complex [LiL]ClO4·2C6H6 is determined by X-ray diffraction analysis.

Ion-selective properties of 1,8-bis [2-(dihydroxyphosphinyl)phenoxy]-3,6-dioxaoctane (H4L3), synthesis and vibrational spectra of copper and zinc complexes with H4L3, and crystal and molecular structure of [Cu(H4L3)(H2O)3][(H2L3)(H2O)]

The ion-selective properties of 1,8-bis[2-(dihydroxyphosphinyl)phenoxy]-3,6-dioxaoctane (H4L3) have been studied and its potentiometric selectivity coefficients have been determined. New complexes [Cu(H4L3)(H2O)3][(H2L3)(H2O)] (I) and Zn(H4L3)(H2L3) · 3H2O, and Cu(H2L3) · 2(H2O) have been synthesized and characterized. The crystal and molecular structure of I has been determined by X-ray crystallography and vibrational spectroscopy. The crystals are monoclinic, a = 10.279(5) Å, b = 26.532(13) Å, c = 8.399(4) Å, β = 99.270(8)°, V = 2260.8(7) Å3, Z = 2, space group Cm, R = 0.0347 for 4325 reflections with I > 2σ(I). Ionic compound I is composed of the [Cu(H4L3)(H2O)3]2+ complex cations and [(H2L3)(H2O)]2− anions. In the cation, the Cu2+ cation located in the m plane is bound to a tetragonal pyramidal (TP) array. The equatorial plane of the TP is formed by two phosphoryl oxygen atoms of the podand (Cu(1)-O, 1.921(2) Å) and two O atoms of two water molecules (av. Cu(1)-O, 1.981(3) Å). The third water molecule is at the axial vertex of the TP at a considerably larger distance (Cu(1)-O, 2.139(3) Å). The anion is of the host-guest type. The host is the deprotonated podand (H2L3)2−, and the guest is the water molecule. The latter is bound to the terminal hydroxyl groups of two phosphoryl groups of the podand by two acceptor hydrogen bonds and to two central ether oxygen atoms of the (H2L3)2− anion by one donor bifurcated hydrogen bond. The cations and anions in the structure are linked by hydrogen bonds to form chains parallel to the c axis.

Zn complex with N-(4′-Benzo-15-crown-5)-2-(amino-N-tosyl)-phenylaldimine: Synthesis, crystal structure, and vibration spectrum

The ZnL2 complex (I) (HL = N-(4′-benzo-15-crown-5)-2-(amino-N-tosyl)phenylaldimine) is synthesized and studied by IR spectroscopy and X-ray diffraction analysis. The crystals are monoclinic: a = 23.139(2) Å, b = 19.931(2) Å, c = 14.604(2) Å, β = 121.20(1)°, Z = 4, space group C2/c, R = 0.751 for 766 reflections with I > 2σ(I). The Zn atom in a molecule of the complex lies on a twofold axis and is coordinated at the vertices of a distorted tetrahedron by four N atoms of two HL ligands (average Zn-N distance 2.024 Å).

Synthesis and ion-selective properties of 1,2-bis[2-((2-diphenylphosphorylmethyl)phenoxy)ethoxy]cyclohexane (L) and its structural analogs. Crystal structure of L

Potentially hexadentate phosphoryl podands 1,2-bis[2-((2-diphenylphosphorylmethyl)phenoxy) ethoxy]cyclohexane (L), 1,2-bis[2-((2-diphenylphosphoryl)phenoxy)ethoxy]cyclohexane (L1), and 1,2-bis[2-((2-diphenylphosphorylmethyl)phenoxy)ethoxy]benzene (L2) are synthesized. Stability constants of complexes formed by L, L1, and L2 with alkali-metal 2,4-dinitrophenolates in mixed THF—CHCl3 solutions (4: 1 by volume) are determined. Electroanalytical characteristics of ion-selective electrodes with hexadentate phosphoryl podands having different structures used as active components of their plasticized membranes are compared for cations of alkali and alkaline-earth metals. The IR spectra are described. The crystal structure of L is studied by X-ray diffraction.

Thermally induced order–disorder transition in crystals of lithium complexes of 1,5-Bis[2-(diphenylphosphorylmethyl)phenoxy]-3-oxapenthane [LiL](ClO4) and [LiL](NCS): Effect of the anion on the temperature of transition

Compounds of 1,5-bis[2-(diphenylphosphorylmethyl)phenoxy]-3-oxapenthane (L) with lithium salts LiXL, where Х– = ClO4, NCS, or I, and LiBrL ⋅ 2H2O, are synthesized. The IR spectra and the thermal behavior of complexes are studied. X-ray diffraction studies of isostructural [LiL](ClO4) (I) and [LiL](NCS) (II) crystals are performed. In the [LiL]+ complex, the ligand coordinates the Li atom by five O atoms, forming an environment in the shape of a trigonal bipyramid [in II at 174 K, the Li–O bonds are1.829(3)–2.341(3) Å]. It is found that crystals I and II undergo a reversible phase transition of the order–disorder type with the change of symmetry (P21/n ↔ P

1,4,10,13-Tetraoxa-7,16- diaza(diphenylphosphinylmethyl)cyclooctadecane (L). As a Prototype of Supramolecular Machine: Synthesis, Crystal Structure, and Vibrational Spectra of the Sodium Thiocyanate Complex with L (NaL)(NCS)

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