Synthesis and Structure of Tetraphenylantimony Nicotinate

Tetraphenylantimony nicotinate was prepared in 91% yield by reaction of pentaphenylantimony with triphenylantimony bis(nicotinate) in toluene. Triphenylantimony bis(nicotinate), in turn, was prepared in 87% yield by oxidative addition of pyridine-3-carboxylic acid to triphenylstibine in ether in the presence of hydrogen peroxide. The structure of tetraphenylantimony nicotinate was determined by single-crystal X-ray diffraction. The Sb atom has a distorted trigonal bipyramidal coordination surrounding with the carboxy group in the axial position. The Sb-C distances are 2.118(1), 2.121(1), 2.130(1), and 2.170(1) Å, and the Sb-O distance is 2.268(1) Å. There is an intramolecular contact between the Sb atom and the carbonyl O atom [3.363(1) Å].     

Tetraphenylantimony Phenylglyoxylate: Synthesis and Structure

Pentaphenylantimony reacts with phenylglyoxylic acid in toluene to give tetraphenylantimony phenylglyoxylate in 88% yield. X-ray data show that the antimony atom in tetraphenylantimony phenylglyoxylate has the trigonal bipyramidal coordination with the oxygen atom in the axial position. The SbÄC distances are 2.114(4), 2.119(4), 2.142(4), and 2.173(4) Å; SbÄO distance, 2.299(3) Å; and C _a SbO angle, 178.7(1)°.     

Tetraphenylantimony Carbonate. Synthesis and Structure

Pentaphenylantimony Ph₅Sb was reacted with triphenylantimony carbonate in toluene to obtain tetraphenylantimony carbonate. The structure of monoclinic crystals of tetraphenylantimony carbonate was studied.     

Tetraphenylantimony Diphenacylphosphinate: Synthesis and Structure

Tetraphenylantimony diphenacylphosphinate was synthesized by reacting pentaphenylantimony with diphenacylphosphinic acid or triphenylantimony bis(diphenacylphosphinate) in toluene (with a yield up to 88%). According to X-ray diffraction data, the antimony atom in tetraphenylantimony diphenacylphosphinate molecule has a trigonal bipyramidal coordination to the axial oxygen atom. The four Sb-C and one Sb-O distances and C_axSbO angle are equal to 2.102(2), 2.104(2), 2.104(2), 2.169(2), 2.347(1) Å and 176.69(5)°, respectively.     

Synthesis and Structure of Tetraphenylantimony Nitrate

The reaction of pentaphenylantimony with triphenylantimony dinitrate in toluene gives tetraphenylantimony nitrate in 99% yield. The X-ray diffraction data show that the antimony atom in the molecule of tetraphenylantimony nitrate has a distorted trigonal-bipyramidal coordination with axial location of the oxygen atom of the nitrate group. The Sb-O, Sb_{a x}, and Sb-C_{e q} bond lengths in two independent molecules of tetraphenylantimony nitrate are 2.498(3), 2.548(2); 2.134(3), 2.138(3); and 2.101(3)-2.112 Å.     

Synthesis and Structure of Tetraphenylantimony N,N-Diethyldithiocarbamate

Tetraphenylantimony chloride was reacted with sodium N,N-diethyldithiocarbamate in water to obtain tetraphenylantimony N,N-diethyldithiocarbamate in 98% yield. According to X-ray diffraction data, the configuration of the molecule of tetraphenylantimony diethyldithiocarbamate is distorted octahedron, and the Sb-S bond lengths are 2.705(2) and 2.771(2) Å.     

Synthesis and Structure of Tetraphenylantimony 2-Furoinate and Benzoate

Tetraphenylantimony 2-furoinate Ph₄SbOC(O)C₄H₃O is synthesized by the reaction of pentaphenyl-antimony with triphenylantimony bis(2-furoinate). The structure of the compound is determined by X-ray diffraction analysis. The Sb atom in the compound has a distorted trigonal-bipyramidal coordination with the phenyl and 2-furoinate groups in the axial positions. The Sb(1)–C(Ph)_eq distances lie in the 2.119(1)–2.121(1) Å interval; the Sb–O(1) and Sb–C(Ph)_ax bond lengths are equal to 2.273(1) and 2.161(1) Å, respectively; and the Sb(1)···(2) intramolecular contact is 3.234(1) Å.     

Synthesis and Structure of New Crystal Modification of Tetraphenylantimony 4-Methylbenzenesulfonate

Tetraphenylantimony arenesulfonates were synthesized by the reaction of pentaphenylantimony with arenesulfonyl chlorides in toluene taken in a molar ratio of 1 : 1 : 2 in air. The structure of tetraphenylantimony 4-methylbenzenesulfonate was determined by X-ray diffraction analysis. The Sb atom has a distorted trigonal-bipyramidal coordination with phenyl and arenesulfonate groups in the axial positions. The Sb–C(Ph)_eq bond lengths vary in the 2.099(2)–2.123(2) Å range, and the Sb–C(41) and Sb–O(1) distances are 2.136(2) and 2.499(1) Å, respectively. The O(1)SbC(4) axial angle is 175.77(5)°.     

Synthesis and Structure of Tetraphenylantimony Methacrylate and Tetraphenylantimony Crotonate and Their Use for the Production of Antimony-Containing Polystyrene

Russian Journal of General Chemistry - Tetraphenylantimony methacrylate Ph4SbO2CC(CH3)=CH2 and tetraphenylantimony crotonate Ph4SbO2CCH=CHCH3 were synthesized by the action of acids on Ph5Sb or on...     

Synthesis and Structure of N,N-Dimethyldithiocarbamates of Tetraphenylantimony and Tetra-p-tolylantimony

Tetraphenylantimony N,N-dimethyldithiocarbamate (I) and tetra-p-tolylantimony N,N-dimethyldithiocarbamate (II) were synthesized via the reaction of tetraarylantimony chloride Ar₄SbCl (Ar = C₆H₅ or C₆H₄Me-4) with sodium N,N-dimethyldithiocarbamate in water. According to the X-ray diffraction data, the tetraarylantimony N,N-dimethyldithiocarbamate molecules have a distorted octahedral configuration. The Sb–S bond lengths are equal to 2.7158(5) Å, 2.7440(5) Å and 2.761(2) Å, 2.8002(2) Å for I and II, respectively.     

Synthesis, Structure, and Reactivity of Model Complexes of Copper Nitrite Reductase

The copper(I) and copper(II) complexes with the nitrogen donor ligands bis[(1-methylbenzimidazol-2-yl)methyl]amine (1-BB), bis[2-(1-methylbenzimidazol-2-yl)ethyl]amine (2-BB), N-acetyl-2-BB (AcBB), and tris[2-(1-methylbenzimidazol-2-yl)ethyl]nitromethane (TB) have been studied as models for copper nitrite reductase. The copper(II) complexes form adducts with nitrite and azide that have been isolated and characterized. The Cu(II)-(1-BB) and Cu(II)-AcBB complexes are basically four-coordinated with weak axial interaction by solvent or counterion molecules, whereas the Cu(II)-(2-BB) and Cu(II)-TB complexes prefer to assume five-coordinate structures. A series of solid state structures of Cu(II)-(1-BB) and -(2-BB) complexes have been determined. [Cu(1-BB)(DMSO-O)(2)](ClO(4))(2): triclinic, P&onemacr; (No. 2), a = 9.400(1) ?, b = 10.494(2) ?, c = 16.760(2) ?, alpha = 96.67(1) degrees, beta = 97.10(1) degrees, gamma = 108.45(1) degrees, V = 1534.8(5) ?(3), Z = 2, number of unique data [I >/= 3sigma(I)] = 4438, number of refined parameters = 388, R = 0.058. [Cu(1-BB)(DMSO-O)(2)](BF(4))(2): triclinic, P&onemacr; (No. 2), a = 9.304(5) ?, b = 10.428(4) ?, c = 16.834(8) ?, alpha = 96.85(3) degrees, beta = 97.25(3) degrees, gamma = 108.21(2) degrees, V = 1517(1) ?(3), Z = 2, number of unique data [I >/= 2sigma(I)] = 3388, number of refined parameters = 397, R = 0.075. [Cu(1-BB)(DMSO-O)(NO(2))](ClO(4)): triclinic, P&onemacr; (No. 2), a = 7.533(2) ?, b = 8.936(1) ?, c = 19.168(2) ?, alpha = 97.66(1) degrees, beta = 98.62(1) degrees, gamma = 101.06(1) degrees, V = 1234.4(7) ?(3), Z = 2, number of unique data [I >/= 2sigma(I)] = 3426, number of refined parameters = 325, R = 0.081. [Cu(2-BB)(MeOH)(ClO(4))](ClO(4)): triclinic, P&onemacr; (No. 2), a = 8.493(3) ?, b = 10.846(7) ?, c = 14.484(5) ?, alpha = 93.71(4) degrees, beta = 103.13(3) degrees, gamma = 100.61(4) degrees, V = 1270(1) ?(3), Z = 2, number of unique data [I>/= 2sigma(I)] = 2612, number of refined parameters = 352, R = 0.073. [Cu(2-BB)(N(3))](ClO(4)): monoclinic, P2(1)/n (No. 14), a = 12.024(3) ?, b = 12.588(5) ?, c = 15.408(2) ?, beta = 101,90(2) degrees, V = 2282(1) ?(3), Z = 4, number of unique data [I >/= 2sigma(I)] = 2620, number of refined parameters = 311, R = 0.075. [Cu(2-BB)(NO(2))](ClO(4))(MeCN): triclinic, P&onemacr; (No. 2), a = 7.402(2) ?, b = 12.500(1) ?, c = 14.660(2) ?, alpha = 68.14(1) degrees, beta = 88.02(2) degrees, gamma = 78.61(1) degrees, V = 1233.0(4) ?(3), Z = 2, number of unique data [I>/= 2sigma(I)] = 2088, number of refined parameters = 319, R = 0.070. In all the complexes the 1-BB or 2-BB ligands coordinate the Cu(II) cations through their three donor atoms. The complexes with 2-BB appear to be more flexible than those with 1-BB. The nitrito ligand is bidentate in [Cu(2-BB)(NO(2))](ClO(4))(MeCN) and essentially monodentate in [Cu(1-BB)(DMSO-O)(NO(2))](ClO(4)). The copper(I) complexes exhibit nitrite reductase activity and react rapidly with NO(2)(-) in the presence of stoichiometric amounts of acid to give NO and the corresponding copper(II) complexes. Under the same conditions the reactions between the copper(I) complexes and NO(+) yield the same amount of NO, indicating that protonation and dehydration of bound nitrite are faster than its reduction. The NO evolved from the solution was detected and quantitated as the [Fe(EDTA)(NO)] complex. The order of reactivity of the Cu(I) complexes in the nitrite reduction process is [Cu(2-BB)](+) > [Cu(1-BB)](+) > [Cu(TB)](+) > [Cu(AcBB)](+).     

Tetraphenylantimony Pentafluorobenzoate and Tetra-p-Tolylantimony Nitrate: Syntheses and Structures

The reactions of pentaarylantimony with antimony derivatives Ar₃SbX₂(Ar = Ph or p-Tol and X = OC(O)C₆F₅or NO₃) afford tetraphenylantimony pentafluorobenzoate (Ph₄SbOC(O)C₆F₅) and tetra-p-tolylantimony nitrate (p-Tol₄SbONO₂). The compounds obtained were structurally characterized by X-ray diffraction analysis. The Sb atom in Ph₄SbOC(O)C₆F₅has a distorted trigonal-bipyramidal environment with an axial perfluorobenzoate group. The trigonal-bipyramidal coordination of antimony in p-Tol₄SbONO₂is strongly distorted, with the O atom of the nitrato group lying in the axial plane.     

Tetraphenylantimony perrhenate and tetraphenylantimony chlorate: Syntheses and structures

The reaction of tetraphenylantimony chloride with sodium perrhenate or potassium chlorate yields tetraphenylantimony perrhenate (I) and tetraphenylantimony chlorate (II), respectively. Complex I was also synthesized from pentaphenylantimony and triphenylantimony diperrhenate in toluene. According to X-ray diffraction, crystals I and II consist of almost regular tetrahedral tetraphenylstibonium cations (CSbC, 109.4(2)°–109.5(7)° in I and 109.1(1)°–109.6(1)° in II) and [ReO₄]^? (OreO, 107.6(3)°–113.3(5)°) and [ClO₃]^? (OClO, 96.3(9)°, 116.4(5)°) anions, respectively. The average Sb-C bond lengths (2.094(3) Å in I, 2.097(2) Å in II) are close to the sum of the covalent radii of the Sb and C atoms. The average distances Re-O in complex I (1.672(4) Å) and Cl-O in complex II (1.315 Å) correspond to multiple bonds.     

Phenylation of Antimony(V) Organic Compounds with Pentaphenylantimony. The Structure of Tetraphenylantimony Chloride

Tetraphenylantimony chloride and bromide were synthesized through the reaction of pentaphenylantimony with diphenylantimony trichloride or tribromide taken at a molar ratio of 2 : 1 in toluene. When the initial compounds were taken at a molar ratio of 1 : 1, triphenylantimony dichloride or dibromide was formed. The phenylation of triphenylantimony sulfate with pentaphenylantimony yielded tetraphenylantimony sulfate. According to the X-ray diffraction data, the antimony atom in the tetraphenylantimony chloride molecule has a distorted trigonal bipyramidal configuration with the chlorine atom in the axial position. The Sb–Cl distance is equal to 2.686(1) and Sb–C distances are equal to 2.113(4) and 2.165(4) Å (av. 2.130 Å).     

Facile Controlled Synthesis of Pd-ZnO Nanostructures for Nitrite Detection

The electrocatalytic characteristics of nanostructures are significantly affected by surface structure. The strict regulation of structural characteristics is highly beneficial for the creation of novel nanocatalysts with enhanced electrocatalytic performance. This work reports a nitrite electrochemical sensor based on novel flower-like Pd-ZnO nanostructures. The Pd-ZnO nanocatalysts were synthesized through a simple hydrothermal method, and their morphology and structure were characterized via field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). Their electrocatalytical performance in the nitrite oxidation reaction was studied via cyclic voltammetry (CV) and the amperometric technique. Compared to pure ZnO and Pd nanoparticles, the Pd-ZnO nanostructures exhibited enhanced electrochemical performance in the nitrite oxidation reaction. In order to investigate the relationships between the structures of Pd-ZnO nanocatalysts and the corresponding electrocatalytic performances, different surface morphologies of Pd-ZnO nanocatalysts were fabricated by altering the solution pH. It was found that the flower-like Pd-ZnO nanostructures possessed larger effective surface areas and faster electron transfer rates, resulting in the highest electrocatalytic performance in the nitrite oxidation reaction. The designed nitrite sensor based on flower-like Pd-ZnO displayed a wide concentration linear range of 1 µM–2350 µM, a low detection limit of 0.2 µM (S/N of 3), and high sensitivity of 151.9 µA mM⁻¹ cm⁻². Furthermore, the proposed sensor exhibited perfect selectivity, excellent reproducibility, and long-time stability, as well as good performance in real sample detection.     

Facile Synthesis of Benzotriazole Derivatives Using Nanoparticles of Organosilane-Based Nitrite Ionic Liquid Immobilized on Silica and Two Room-Temperature Nitrite Ionic Liquids

Nanoparticles of organosilane-based nitrite ionic liquid immobilized on silica, 1-butyl-3-methylimidazolium nitrite, and 1-(3-trimethoxysilylpropyl)-3-methylimidazolium nitrite were used as effective reagents for the preparation of benzotriazole derivatives from 1,2-diaminobenzenes at room temperature under mild solvent-free conditions. These ionic liquids play as nitrosonium sources in this procedure.1,2-Diaminobenzene derivatives have been treated with ionic liquids to give the related diaminobenzenes in very good to excellent yields in short reaction times.

Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the full experimental and spectral details.     

Synthesis and Structure of Tetraphenylantimony Phenoxyacetate and Ethylmalonate Ph4SbOC(O)R (R = CH2OPh and CH2C(O)OC2H5)

Tetraphenylantimony phenoxyacetate (I) was synthesized by reacting pentaphenylantimony with phenoxyacetic acid (at a molar ratio of 1 : 1) in toluene. Tetraphenylantimony ethylmalonate (II) was synthesized from triphenylantimony and malonic ether in the presence of hydrogen peroxide (1 : 1 : 1) in diethyl ether. According to X-ray diffraction data, Sb atoms in compounds I and II have a distorted trigonal bipyramidal coordination to the axial oxygen atoms. The axial OSbC_ax angles and Sb-C_ax distances are, respectively, 176.31(6)° and 2.177(2) Å for I and 179.40(4)° and 2.162(1) Å for II. The Sb-C_eq distances lie in the intervals of 2.108(2)-2.127(2) Å for I and 2.117(1)-2.128(1) Å for II. In compounds I and II, the Sb-O bond lengths are equal to 2.235(1) Å and 2.250(1) Å, respectively, and the intramolecular contacts Sb··· are equal to 3.402(2) Å and 3.282(1) Å, respectively.     

1,5-苯并硫氮杂-α,α-二甲基-β-内酰胺衍生物的合成、表征及晶体结构

利用异丁酸乙酯、异丁酸异丙酯、异丁酸薄荷醇酯和LDA作用形成烯醇锂盐，然后和1,5-苯并硫氮杂     

Synthesis and Structure of Diphenoxytriphenylantimony

Diphenoxytriphenylantimony was synthesized via the reaction of triphenylantimony dibromide with sodium phenolate, and its structure was determined using X-ray diffraction analysis. The Sb atom exhibits trigonal bipyramidal coordination. The Sb–C bond lengths are equal to 2.095(2), 2.121(2), and 2.122(2) Å the Sb–O distances and the axial OSbO angle are equal to 2.056(1), 2.046(1) Å and 179.11(5)°, respectively.     

Synthesis and Structure of B-Carboranylphosphonates

Abstract

Photolysis of bis(m-carboran-9-yl)mercury and bis(p-carboran-2-yl)mercury in trimethylphosphite leads to the formation of dimethyl ethers of (m-carboran-9-yl)- and (p-carboran-2-yl)-phosphonic acids: