Synthesis and properties of functional derivatives ofN′-phosphoryl- andN′-phosphonoyldiazeneN-oxides; molecular structure ofN-(2,2-dimethyl-5-nitro-1,3-dioxan-5-yl)-N′-[methoxy(phenyl)phosphoryl]diazeneN-oxide

Methods for the synthesis of polyfunctionalN-phosphoryl- andN-phosphonoyldiazeneN-oxides containing hydroxyl, acetoxyl, and nitrate groups, and dibromoallyl and dibromopropyl fragments have been developed. The molecular structure ofN-(2,2-dimethyl-5-nitro-1,3-dioxan-5-yl)-N-[methoxy(phenyl)phosphoryl)diazeneN-oxide was established by X-ray structural analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1284–1289, July, 1994.     

Influence of the Size of Aromatic Chelate Ligands on the Structures of Cadmium(II) Tetracarboxylates Polymers: From 2D Layered Network to 3D Metal‐Organic Framework

To determine the influence of the size of the aromatic chelate ligands on the frameworks of metal tretracarboxylate polymers, two new coordination polymers [Cd(btc)_0.5 (2,2′‐bpy)] ( 1 ) and [Cd(btc)_0.5(phen)]·H₂O ( 2 ) (H₄btc = biphenyl‐3,3′,4,4′‐tetracarboxylic acid, 2,2′‐bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline) have been synthesized under similar hydrothermal conditions. In complex 1 , the dimeric Cd₂ units are linked by bridging btc^4? ligand to form a 2D layered network, whereas complex 2 possesses a 3D metal‐organic framework consisting of the dimeric Cd₂ units. The differences of two metal‐organic frameworks demonstrate that the size of the rigid aromatic chelate ligands have an important effect on the structures of their complexes. Additionally, the two complexes show strong fluorescence in the solid state at room temperature.     

Solid state coordination chemistry of copper(II)/α-hydroxycarboxylato/2,2′-bipyridine systems

Four new two-ligand complexes of copper(II) with 2,2′-bipyridine and one of three different α-hydroxycarboxylic acids (lactic, H₂LACO; 2-methyllactic, H₂MLACO; and mandelic, H₂MANO) were prepared. Complexes 1–3 of general formula [Cu(HL)₂(bipy)]·nH₂O (HL=monodeprotonated acid), were characterized by elemental analysis, IR, electronic and EPR spectroscopy, magnetic measurements and thermogravimetric analysis. Complexes 1 (HL=HLACO, n=2), 2 (HL=HMLACO, n=1) and 3a (the result of attempted recrystallization of 3, of formula [Cu(HMANO)(bipy)₂](HMANO)·H₂MANO·CH₃CN were studied by X-ray diffractometry. The copper atom is in an elongated, tetragonally distorted octahedral environment in 1 and 2 and in 3a has a coordination polyhedron intermediate between a square pyramid and a trigonal bipyramid, as evaluated in terms of the parameter τ. In 1 and 2 the α-hydroxycarboxylato ligand is bidentate and monoanionic but in 3a there are three forms: a monodentate monoanion, a monoanionic counterion, and a neutral molecule.     

Reaction ofN-(3,3,3-trifluoro-2-trifluoromethylprop-1-enyl)dimethylamine with MgSO4·7H2O. Synthesis of 4,4-difluoro-5-trifluoromethyl-2-(2,2,2-trifluoro-1-trifluoromethylethyl)-4H-1,3-dioxine andcis/trans-3-dimethylamino-2-trifluoromethacryloyl fluoride

4,4-Difluoro-5-trifluoromethyl-2-(2,2,2-trifluoro-1-trifluoromethylethyl)-4H-1,3-dioxine andcis/trans-3-dimethylamino-2-trifluoromethacryloyl fluoride were obtained by reaction ofN-(3,3,3-trifluoro-2-trifluoromethylprop-1-enyl)dimethylamine with MgSO₄·7H₂O. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1069–1071, May, 1997.     

The first indium-organic two-dimensional layer network with rhombus grids

The indium(III)-organic compound [In(HBtc)₂(4,4′-bpy)](4,4′-Hbpy)(H₂O)_0.5 (Btc=1,3,5-benzenetricarboxylate, 4,4′-bpy=4,4′-bipyridine) has been synthesized under hydrothermal condition and characterized by IR, fluorescent spectroscopy, TGA and single-crystal X-ray diffraction analyses. The compound crystallizes in monoclinic, space group P2(1)/c, a=17.0884(2) Å, b=12.28390(10) Å, c=17.9456(4) Å, β=104.1920(10)°, V=3652.03(10) Å³, Z=4, R₁=0.0572 and wR₂=0.1116 [I>2σ(I)]. All the indium atoms in the compound are hepta-coordinated and link 1,3,5-benzenetricarboxylate forming a 2-D layer structure with rhombus grids.     

New optically active organoantimony (BINASb) and bismuth (BINABi) compounds comprising a 1,1′-binaphthyl core: synthesis and their use in transition metal-catalyzed asymmetric hydrosilylation of ketones

Racemic 2,2′-bis[diarylstibano]-1,1′-binaphthyls [(±)-BINASbs] and 2,2′-bis[di(p-tolyl)bismuthano]-1,1′-binaphthyl [(±)-BINABi], which are the antimony and bismuth congeners of BINAP, have been prepared from 2,2′-dibromo-1,1′-binaphthyl (DBBN) via 2,2′-dilithio-1,1′-binaphthyl intermediate by treatment with the appropriate metal halides [(p-Tol)₂SbBr, Ph₂SbBr and (p-Tol)₂BiCl]. The optical resolution of the (±)-BINASbs could be achieved via the separation of a mixture of the diastereomeric Pd-complexes derived from the reaction of (±)-BINASbs with di-μ-chlorobis{(S)-2-[1-(dimethylamino)-ethyl]phenyl-C¹,N}dipalladium(II). Optically active (R)-BINASb and (R)-BINABi could be also obtained from optically active (R)-DBBN by the same procedure. The enantiopure BINASbs have been shown to be effective chiral ligands for the rhodium-catalyzed asymmetric hydrosilylation of ketones.     

Thermal and other properties of complexes of Mn(II), Co(II) and Ni(II) with 2,2'-bipyridine and trichloroacetates

Complexes of the general formulae Mn(2-bpy)₂(CCl₃COO)₂, Co(2-bpy)₂(CCl₃COO)₂·H₂O and Ni(2-bpy)₂(CCl₃COO)₂·2H₂O (where: 2-bpy=2,2'-bipyridine) have been prepared and characterized by VIS and IR spectroscopy, conductivity and magnetic measurements. The thermal properties of complexes in the solid state were studied under non-isothermal conditions in air atmosphere. During heating the complexes decompose via different intermediate products to the oxides Mn₃O₄, CoO and NiO. A coupled TG-MS system was used to detection the principal volatile products of thermal decomposition and fragmentation processes of obtained compounds. The principal volatile products of thermal decomposition of complexes are: H₂O⁺, CO₂ ⁺, Cl₂ ⁺ and other. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis of pyridine and 2,2′-bipyridine derivatives from the aza Diels-Alder reaction of substituted 1,2,4-triazines

Amidrazone 1a and the tricarbonyl derivatives 2b-d reacted in boiling ethanol in the presence of 2,5-norbornadiene 5 giving the pyridine derivatives 6b-d respectively (59-72%) and in the presence of 2,3-dihydrofuran 7 yielding the lactones 10b-d (39-44%). The 2,2′-bipyridine derivatives 6e-g were similarly obtained in good yield (81-87%) from the reaction of amidrazone 1b and tricarbonyl derivatives 2b-d in the presence of 2,5-norbornadiene 5.     

Fast and highly selective determination of cyanide with 2,2-dihydroxy-1,3-indanedione

A very simple, accurate, fast, selective and sensitive assay of cyanide based on its reaction with 2,2-dihydroxy-l,3-indanedione at basic pH is proposed. As little as 0.01 μg ml⁻¹ of cyanide can be determined. The molar absorptivity may reach 5.1–8.0×10⁴ l mol⁻¹ cm⁻¹ depending on the reaction conditions. Thus, 1 ml of sample solution is mixed with 500 μl of 5 mg ml⁻¹ solution of 2,2-dihydroxy-1,3-indanedione monohydrate in 2% sodium carbonate. The absorbance of the purple color is measured at 510 nm in 1-cm glass cuvettes, 10–15 min after mixing the reagents. The procedure could also be used to identify free CN⁻ in natural waters and hydrocyanic acid in the environment.     

消旋的有机二磺酸三邻菲咯啉锌配合物(英)

Compound [Zn(phen)₃][BDA] (1) (BDA=6,6′-dibromo-2,2′-dimethoxy-1,1′-binaphthylene-4,4′-disulfonate, phen= 1,10-phenanthroline) composes of the anion part (racemic-(R,S)-6,6′-dibromo-2,2′-dimethoxy-1,1′-binaphthylene-4,4′-disulfonate ) and the cation part which consists of a racemic octahedrally coordinated zinc center defined six nitrogen atoms from three phen rings to form an inorganic chirality that can be resolution by chiral organic ligand, the 3D framework was formed through the strong H-bonding interaction between sulfonate and water. CCDC: 277924.