Synthesis,Structure and Properties of C(X)NHP(Y) Fragment Containing Compounds

Abstract

N-(thio)carbonyl(thio)amidophosphate, their open-chain and crown-containing analogues with a C (X) NHP (Y) fragments are associated with intermolecular hydrogen bonds as C=X…H-N and P=Y…H-N or intramolecular hydrogen bonds of N-H…O(macrocycle). These compounds easily enter into alkylation reaction, are added according to C=N bonds of activated imines, take part in O → S and S → O exchanging reactions.     

Macroheterocyclic Compounds with Thiadiazole Fragments. Synthesis and Properties

The reactions of 1-imino-2-phenyl-1H-inden-3-amine with 3,5-diamino-1,2,4- and 2,5-diamino-1,3,4- thiadiazoles were used to synthesize linear 1: 2 and 2: 1 condensation products, as well as symmetrical macroheterocyclic compounds. The synthesized compounds were characterized by IR, UV, and ¹Н NMR spectroscopy.     

Macrocyclic Compounds with 2-Phenylindene Fragments. Synthesis and Properties

By the reaction of 1-imino-2-phenyl-1H-indene-3-amine with 1,4-naphthylenediamine and 1,4-diaminonaphthalenesulfonic acid linear products of 1 : 2 and 2 : 1 condensation as well as macrocyclic compounds were synthesized.     

Synthesis,Complexes and Metal Extraction Ability of R1R2NC(X)NHP(Y)(0Ph)2

Abstract

The new 1,1-disubstituted 3-diphenoxy(thio)phosphoryl-(thio)ureas, R¹R²NC(X)NHP(0Ph)₂, HA, with X,Y = O,S, were synthesized by addition of secondary mines to the corresponding P-iso(thio)cyanates. This reaction is reversible if X,Y = S. (PhO)₂P(Y)Cl reacts with H₂NC(X)NR₂ in the presence of an HCl acceptor only if X,Y a 0. Side reactions are observed. Phosphorylated derivatives of biuret were isolated from such a reaction mixture.     

Nb2Y2X6, a Novel Type of NbIV Compounds with Cross-linked Nb2 and Y2 Dumbbells (Y = Se,Te; X = Br,I)

The compounds Nb₂Se₂Br₆, Nb₂Te₂Br₆, and Nb₂Te₂I₆ were prepared from the elements in sealed quartz ampoulès at 1073 K. The crystalline solids, exhibiting a metallic lustre, are insensitive against moisture and oxygen. All compounds undergo several reversible thermal transitions with temperature (DTA). Beside binary halides only NbYX₃ is present in the gas phase. The structures consist of one-dimensional infinite chains of halogen bridged Nb₂(Y₂)X₄ units containing single side-on bonded Nb₂ and Y₂ dumbbells forming a quasi tetrahedral Nb₂Y₂ cluster (Nb? Nb ? 283.2; 287.5; 293.2 pm; Se? Se ? 230.5 pm; Te? Te ? 267.0; 268.5 pm). The structural and magnetic properties clearly prove the formal oxidation states Nb⁴⁺ and Y^1?, unexpected from stoichiometry. (Structural data: all P2/a (No. 13); Nb₂Se₂Br₆: a = 1254.0(12); b = 689.7(10); c = 662.4(10) pm; β = 98.9(1)°; Z = 2; 1274 hkl; R = 0.066. Nb₂Te₂Br₆: a = 1259.7(13); b = 713.5(9); c = 667.0(9) pm; β = 97.6(1)°; 1557 hkl; R = 0.043. Nb₂Te₂I₆: a = 1347.3(3); b = 742.9(2); c = 714.1(2) pm; β = 98.52(2)°; 1540 hkl; R = 0.026).     

Complexing of Organoaluminum Compounds with Polyethers and Polyacetals

This work is concerned with the study of the complexing reaction between the low molecular weight V-acceptor, diethylaluminum chloride (DC), and polymeric donors containing oxygen, such as poly(ethylene oxide) (PEO), polypropylene oxide) (PPO), polytetrahydrofuran (PTHF), polyformal-dehyde (PF), poly(phenylene oxide) (PPO), polydioxolan (PDO), and polytrioxocan (PTO). Three types of complexes, 1:1, 2:1, and 1:2, were detected in solution. In the case of PEO, the thermodynamical parameters of the 1:1 complex formation are ΔH₁ = ?23.3 ± 0.5 kcal/mole, K¹ = (5 ± 2) × 105 liter/mole, ASi = ?51.5 ± 2.4 eu, while those of the 1:2 complex formation (0.2A1) from the 1:1 adduct are AH = -18.5 ± 0.6 kcal/mole, K = 0.9 ± 0.3 liter/mole, AS = ?62.3 ± 2.9 eu. Two structures were found in the case of 1:1 polymer-acceptor complexes.     

Influence of Metal Complexing on the Nonlinear-Optical Properties of Compounds with High Molecular Symmetry

Coordination bonding of 1,5-diphenylpentadienone was studied with the aim to prepare compounds exhibiting third-order nonlinear optical properties. The volume resistivity of these compounds was studied as influenced by the third-order nonlinear susceptibility tensor.     

Complexing Properties of Scandium(III) in Alkaline Medium

The behavior of scandium compounds in going from alkaline solutions to carbonate and hydrocarbonate solutions was studied. The possibility of coprecipitation of scandium(III) complex carbonate with zinc oxide was examined.     

三配位五价磷化合物[R—P（=X）（=Y）的结构及化学性质

综述了三配位五价磷化合物的结构犊 征及其所具有的加成反应，络合反应，磷中心的亲电反应等化学性质。参考文献２２篇。     

A method of describing rotation around (Y)C(sp2)-X bonds (X = C,O, Y = C (sp2), O) in molecular mechanics

Institute for Organic and Physical Chemistry, Kola Branch, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 5, pp. 52–56, September–October, 1991.     

稠环类苯化合物的化学键性质

用HF和DFT的B3LYP方法,在6-31G*水平上,首次对XmAlnNnHm(X=Cl,H;n=3,5,7,8,10,12;m=3,4,5,6)稠环类苯化合物的几何构型、红外光谱和化学键性质进行了研究,并与相应的XmC2nHm稠环化合物苯、萘、菲、芘、苝和蒄的结构作了比较.结果表明,XmAlnNnHm与XmC2nHm具有相同的几何构型,随着配位原子与骨架原子数之比R的增大,Al-N键能逐渐增大,键长逐渐减小;配位原子X对骨架化学键Al-N或C-C的影响较小.     

Synthesis and Study of Acid-Basic Properties of Ti(IV) and Zr(IV) Phosphates Immobylized in the Matrix of Clinoptilolite

Abstract

By combination of the ionexchange and ionic-molecular layering methods [1], the synthesis of natural zeolite derivatives (clinoptilolite) containing in its composition nano-size fragments of Ti(IV) and Zr(IV) phosphates was performed. It was determined by the X-Ray method, that the phosphates of Ti(IV) and Zr(IV) replicate crystal lattice of zeolite, manifesting in enhancing the line's intensity on X-Ray patterns. The Brensted's and Lewis's spectra of acidic centers distributions were obtained by Hammett's indicator spectrophotometric method [2] in the interval of pK, values from -4.4 to 14.2, which have shown that P(V) of the derivatives is represented mainly by HPO₄- and H₂PO₄-groups, with predomination of these latter. It is shown that the force of Brensted's acidic centers, influenced by H₂PO₄-groups. remains at the level of H₂PO_(aq)-anion, and the force of the centers due to HPO₄-groups shifts into alkaline region, about 0,5 unit of pK. The strong acidic Lewis's centers were detected at the levels of pK, from 0 to -4.0. The spectra of Ti(IV) and Zr(IV) phosphates is presented in (1) and (2) respectively. A set of the acquired results makes possible a suggestion about using P(V)-containing derivatives in processes which are catalyzed both with Brensted's and Lewis's centers participation.     

Two New Carbaalanes: Compounds with an Al(7)C(5) and a

The hydroalumination of aluminum ethynides leads to the formation of carbaalanes as a new class of compounds, which have clusters exclusively formed by carbon and aluminum atoms. Two novel carbaalanes with Al(7)C(5) and Al(7)C(4) clusters are described-the latter is a remarkable analogue of closo-[B(11)H(11)](2-) with respect to its structure and the number of cluster electrons.     

Synthesis of Macrocyclic Phosphites and Thiophosphates with Complexing Properties

2-Alkoxy (or 2-alkylamino)-1,3-dioxa-6,9-diaza-2-phospha-cycloundecanes and their 2-thiono derivatives have been prepared by reaction of alcohols and diols, (or amines and diamines) with a bicyclic 1,3,2-oxazonia-phospholane salt and subsequent sulfurization.     

Acid and Complexing Properties of Tetraazaporphyrins

In this review, the kinetic regularities underlying the formation and stability of acid–base tetraazaporphyrin complexes with nitrogen bases in benzene (chlorobenzene) are considered. The relationships between the structure of protolytes and their reactivities are discussed. The role of the acid–base interactions in the reaction of magnesium acetate or acetylacetonate with tetrahalogen- and octaphenyl-substituted tetraazaporphyrins in the nitrogen-containing base–benzene system was revealed. The possible mechanisms of the processes under study are considered and a relatioship is established between the reaction rate constants and structural changes in a solution.     

Synthesis and Complexing Ability of Hyperbranched Polyester Polyols Containing Carboxylic Acid Fragments

New hyperbranched polyester polycarboxylic acids containing terminal propanoic and acrylic acid fragments have been synthesized. According to the IR spectral data, the complexation of polydentate hyperbranched polyester polycarboxylic acids with Co(II), Ni(II), and Cu(II) ions involves chelation and bidentate bridging coordination by the terminal carboxy groups. All Co(II), Ni(II), and Cu(II) complexes with the obtained polyester polypropanoic acids are characterized by octahedral geometry of the coordination entity (MO₆). The Co(II), Ni(II), and Cu(II) complexes with polyester polyacrylic acids have tetrahedral configuration of the coordination entity (MO₄).     

Complexes of Co(II) and Zn(II) with N-(Thio)phosphorylthioureas AdNHC(S)NHP(O)(OiPr)2 and MeNHC(S)NHP(S)(OiPr)2

The reaction of the potassium salt of the N-(thio)phosphorylated thioureas AdNHC(S)NHP(O)(OiPr)₂ (HL^I , Ad = Adamantyl) and MeNHC(S)NHP(S)(OiPr)₂ (HL^II ) with Co(II) and Zn(II) in aqueous EtOH leads to [ML^I,II ₂] chelate complexes. They were investigated by UV-vis, ¹H and ³¹P NMR spectroscopy, and microanalysis. The molecular structures of [ML^I ₂] were elucidated by single crystal X-ray diffraction analysis. The metal centers in both complexes are found to be in a distorted-tetrahedral O₂S₂ environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated L^I ligands. The photoluminescence properties of [ZnL^II ₂] are also reported.     

Syntheses and Complexing Properties of Polyethers

Diaza-18-crown-6 with two 8-hydroxyquinolines as side arms show high selective complexing ability with metal ions^[1,2] and with two aminophenols exhibit strange property^[3]. 8 diaza-18-crown-6 ethers containing sidearms^[4] and 7 podands were synthesized. Their complexing ability with metal ions were studied, the results show that they present high complexing capability for metal ions. The polyethers containing 8-hydroquinoline fragment show high selectivities for Hg²⁺,Ni²⁺ and their complexes with Eu³⁺ and Tb³⁺ show strong luminescence.