2-methoxy-5-bromophenyl antimony compounds. Synthesis and structure

Reaction of 2-methoxy-5-bromophenyllithium with antimony trichloride in diethyl ether affords tris-(2-methoxy-5-bromophenyl)antimony benzene solvate I. Its structure and chemical transformations into the new antimony aryl derivatives were studied.     

Tris(2-methoxy-5-chlorophenyl)antimony: Synthesis and Oxidative Addition Reactions

Russian Journal of General Chemistry - The reaction of 2-methoxy-5-chlorophenyllithium with SbCl3 (3 : 1) in diethyl ether has afforded tris(2-methoxy-5-chlorophenyl)antimony, which has been...     

Synthesis and Structure of Tris(2-methoxy-5-chlorophenyl)antimony Diarylcarboxylates and Diarenesulfonate

Russian Journal of General Chemistry - The reactions of tris(2-methoxy-5-chlorophenyl)antimony with 3,5-dinitrobenzoic, 2,4-dichlorophenoxyacetic, and 2,4-dimethylbenzenesulfonic acids in the...     

Synthesis and structural features of tris(5-bromo-2-methoxyphenyl)antimony bis (cyclopropanecarboxylate)

Reaction of tris(5-bromo-2-methoxyphenyl)antimony with cyclopropanecarboxylic acid in the presence of hydrogen peroxide (1:2:1 mol) results in tris(5-bromo-2-methoxyphenyl)antimony bis(cyclopropanecarboxylate) I. The structure of the resulting complex was proved by the XRD analysis.     

Synthesis and structure of bis(monohaloacetates) of tris(5-bromo-2-methoxyphenyl)antimony

Tris(5-bromo-2-methoxyphenyl)antimony bis(monohaloacetates) [(5-Br)(2-MeO)C₆H₃]₃Sb[OC(O)CH₂X]₂, X = Cl (I), Br (II), I (III) have been synthesized by the reaction of tris(5-bromo-2-methoxyphenyl)antimony with chloro-, bromo-, and iodoacetic acids in the presence of hydrogen peroxide. According to X-ray analysis the antimony atom in I–III has a distorted trigonal-bipyramidal coordination.     

Tris(2,6-dimethoxyphenyl)antimony Diazide: Synthesis and Structure

Tris(2,6-dimethoxyphenyl)antimony diazide has been synthesized and characterized by X-ray diffraction. The antimony atoms in four crystallographically independent molecules have a distorted trigonal pyramidal coordination. Axial angles range within 174.57°–178.95°.     

Tris(3-fluorophenyl)antimony Dihalides: Synthesis and Structure

Russian Journal of General Chemistry - Tris(3-fluorophenyl)antimony dichloride, dibromide, and diiodide were obtained by the reaction of tris(3-fluorophenyl)antimony with chlorine, bromine, and...     

Synthesis and structural features of tris(5-bromo-2-methoxyphenyl)antimony dicarboxylates

Tris(5-bromo-2-methoxyphenyl)antimony bis(4-nitrophenylacetate) (I), tris(5-bromo-2-methoxyphenyl)antimony bis(2-methoxybenzoate) (II), and tris(5-bromo-2-methoxyphenyl)antimony bis(phenylpropiolate) (III) have been synthesized via the reaction between tris(5-bromo-2-methoxyphenyl) antimony and 4-nitrophenylacetic acid, 2-methoxybenzoic acid, and phenylpropiolic acid, respectively, in the presence of hydrogen peroxide (molar ratio: 1: 2: 1). According to X-ray diffraction data, the antimony atom in molecules of complexes I–III has a distorted trigonal bipyramidal coordination. The OSbO axial angles and the CSbC bond angles in the equatorial plane are 173.27(15)°, 172.96(11)°, 172.99(10)°, and 115.5(2)°–123.3(2)°, 108.81(16)°–129.32(17)°, and 110.66(17)°–127.91(17)°, respectively. The Sb-O bond lengths are 2.092(4) and 2.115(4)Å in I, 2.088(3) and 2.097(2) Å in II, and 2.096(3) and 2.120(3) Å in III. The Sb-C bonds range within 2.095(6)–2.123(6) Å in I, 2.107(4)–2.117(4) Å in II, and 2.097(4)–2.116(4) Å in III. Complexes I, II, and III are observed to have intramolecular Sb…OCH₃ contacts (3.169–3.226, 3.134–3.174, and 3.147–3.196 Å, respectively) in addition to Sb…O=C interactions (3.121, 3.139Å; 2.944, 3.038 A0; 3.111, 3.120 Å).     

Triphenyl- and Tris(para-tolyl)antimony Dicarboxylates: Synthesis and Structures

Russian Journal of Coordination Chemistry - The reactions of tris(para-tolyl)antimony (4-МеС6H4)3Sb with chloroacetic acid and of triphenylantimony Ph3Sb with...     

Tris(5-bromo-2-methoxyphenyl)bismuth bisbenzenesulfonate solvate with toluene: Synthesis and structure

Tris(5-bromo-2-methoxyphenyl)bismuth bisbenzenesulfonate, which crystallizes from toluene in the solvate form (5-Br-2-MeOC₆H₃)₃Bi(OSO₂Ph)₂ ? TolH (I), has been synthesized by the reaction between tris(5-bromo-2-methoxyphenyl)bismuth and benzenesulfonic acid in the presence of hydrogen peroxide (1: 2: 1 mol/mol/mol) in ether. A crystal contains two types of crystallographically independent molecules (a and b), in which bismuth atoms have a trigonal bipyramidal coordination to benzenesulfonate substituents in axial positions. The axial OBiO angle is 175.4(3)° (Ia) and 175.5(3)° (Ib), and the equatorial CBiC angles are 111.2(3)°, 122.0(4)°, 126.7(4)° (Ia) and 111.3(4)°, 123.3(3)°, 125.2(4)° (Ib). The Bi–C distances are 2.189(9), 2.198(9), 2.200(10) Å (Ia) and 2.198(9), 2.202(9), 2.209(9) Å (Ib). The Bi–O bond lengths are 2.274(8), 2.306(8) Å (Ia) and 2.248(8), 2.303(8) Å (Ib). Intramolecular contacts between the bismuth atom and the oxygen atoms of methoxy and sulfonate groups take place in molecules.     

Tris(bis(trimethylsilyl)amido)samarium: X-ray structure and DFT study

The compound Sm[N(SiMe(3))(2)](3) has been investigated experimentally by X-ray crystallography and computationally by DFT methods. The structure is analogous to that of other tris[bis(trimethylsilyl)amido]lanthanides, featuring positional disorder of the metal atom above and below the plane defined by the three N donor atoms, resulting in a trigonal pyramidal configuration. One of the methyl groups of each amido ligand is placed above the apex of the pyramid at close distance to the metal center suggesting the presence of agostic interactions. The DFT calculations have been carried out on the real molecule and on a Si[N(SiH(3))(SiH(2)Me)](3) model where the unique Me group was placed above the apex of the pyramid to probe the agostic interaction. In both cases, the optimized geometry reproduces very well the experimental structure and indicates the presence of beta-Si-C agostic interactions. A comparison of the optimized geometries obtained in the presence/absence of the Sm d and the Si d orbitals serves to illustrate the relevance of these orbitals for (i). the establishment of the pyramidal configuration at Sm, (ii). the Sm-N bond length, and (iii). the Sm-(beta-Si-C) bond length. The bonding analysis, which was carried out by both Mulliken and NBO methods, not only confirms the importance of the metal d orbitals for the Sm-N and Sm-(beta-Si-C) chemical bonding but also illustrates the relevance of electrostatic terms in the agostic interaction. Sm-N and N-Si pi bonding is present according to the bonding analysis but is not important for enforcing the planar configuration at N, nor the pyramidal configuration at Sm.     

Synthesis of new antimony(III) and bismuth(III) aryl compounds: Crystal and molecular structure of tris(5-bromo-2-methoxyphenyl)antimony

Tris(5-bromo-2-methoxyphenyl)antimony (I) (yield, 85%) and tris(5-bromo-2-methoxyphenyl)bismuth (II) (yield, 81%) were obtained by reacting 5-bromo-2-methoxyphenyllithium with antimony(III) chloride and bismuth(III) chloride, respectively. According to X-ray diffraction data, the antimony atom in I is highly coordinated. The Sb-C bonds lengths are 2.160(1) Å, 2.163(1) Å, and 2.157(2) Å; the Sb…O distances are 2.985(1) Å, 3.051(1) Å, and 3.052(1) Å. The CSbC bond angles vary in the range of 92.19(6)°-94.52(6)°. Molecules of I are linked via Sb(A)…Br(B) intermolecular contacts (3.742(2) Å) to form polymer chains.     

Synthesis and structure of triphenylbismuth bis(2-phenylaminobenzoate)

Interaction of triphenylbismuth with phenylanthranilic acid in the presence of hydrogen peroxide yields triphenylbismuth bis(2-phenylaminobenzoate), in which bismuth atoms have a distorted trigonal bipyramidal coordination with phenyl ligands in equatorial positions. The bond lengths (Å) are as follows: Bi-C, 2.193(5), 2.200(4), and 2.200(4); Bi-O, 2.252(4) and 2.300(4). Intramolecular hydrogen bonds N-H?O(=C) (H?O, 1.91, 1.97 Å; N?O, 2.634(9), 2.667(9) Å) and donor-acceptor interactions Bi?O(=C) (2.790(5) and 2.838(5) Å) exist in the molecule.     

3-氯-4-二苄胺基-5-甲氧基-2(5H)-呋喃酮的合成与晶体结构

在THF溶液中合成了标题化合物3-氯-4-二苄胺基-5-甲氧基-2(5H)-呋喃酮,并用FT-IR、UV-Vis、1HNMR、13C NMR、MS、元素分析和X-射线衍射等进行了表征。结果表明此化合物属正交晶系,空间群为Pbca,晶胞参数为:a=15.891(16),b=11.126(11),c=19.778(19),α=β=γ=90°,V=3497(6)3,Z=8,Dc=1.306Mg/m3,μ=0.234 mm-1,F(000)=1440。在化合物的分子结构中,两个苯环几乎垂直于呋喃酮平面,且它们与呋喃酮平面的两面角分别为89.38°和88.19°。     

Tris(1-adamantanecarboxylato)bismuth(III): Synthesis and structure

Tris(1-adamantanecarboxylato)bismuth(III) was synthesized by reacting triphenylbismuth with 1-adamantanecarboxylic acid in toluene. The bismuth atom in tetramer {Bi[OC(O)C₁₀H₁₅]₃}₄ is coordinated by 10 oxygen atoms of bidentate-chelating and two types of chelate-bridging adamantanecarboxylate ligands (Bi-O, 2.191–2.955 and 3.634 Å).     

(±)-金锦香酸二甲酯甲醚的合成

本文以呋喃甲酸甲酯为原料, 经羟烷基化反应, 醇解反应和O-甲基化反应合成(±)-金锦香酸二甲酯甲醚。同时, 还发现了制备2-乙烯基呋喃衍生物的新方法。     

Synthesis and structure of 5-methoxy-4-methylbenzopsoralen

5-Methoxy-4-methyl-2H-benzofuro[3,2-g]benzo-1-pyran-2-one was synthesized and its crystal structure was determined and compared with the optimal conformation arrived at by MM and AM1 theoretical calculations. The latter indicated that the tetracyclic skeleton is planar with total length (C2–C8) 9.23 å, and that the line joining the conters of the terminal-benzene and furan rings makes an angle of 30.5 with that joining the centers of the three rings of psoralen. The electronic properties of the reactive double bond in the pyran ring of1 are similar to those of simpler psoralens.     

Synthesis and structure of bis(2-phenylethyl) phosphine selenide

Bis(2-phenylethyl)phosphine selenide was obtained with 86% yield from bis(2-phenylethyl)phosphine and selenium. XRD, IR, UV, and multinuclear NMR spectroscopic studies revealed that the phosphorus atom in the bis(2-phenylethyl)phosphine selenide molecule is four-coordinated irrespective of the phase state (crystals or solution).     

Synthesis, structure, and NO-donor activity of bis(5-nitropyridine-2-thiolato)tetranitrosyliron

A new method is developed for the synthesis of the binuclear iron tetranitrosyl complex with 5-nitropyridine-2-thiolate, [Fe₂(SC₅H₃N₂O₂)₂(NO)₄] (I), from 2,2??-dithiobis(5-nitropyridine) and hydrazine hydrate in an aqueous-alcohol solution followed by the replacement of the thiosulfate ligands in an aqueous solution of salt Na₂[Fe₂(S₂O₃)₂(NO)₄] · 4H₂O by functional 5-nitropyridine-2-thiolates. It is established by the X-ray diffraction method that the complex has the structure of the ??-SR type and crystallizes as two polymorphs. The Moessbauer spectral parameters at 293 K (quadrupole splitting ??E _Q = 1.243(1) mm/s, isomeric shift ??_Fe = 0.095(1) mm/s, and absorption line width ?? = 0.263(1) mm/s) for studied compound I are similar to the isoelectronic complexes with thiophenoxide, pyridyl-2-thiolate, and pyrimidyl-2-thiolate. According to the electrochemical analysis data, complex I is a more efficient donor of NO in hydrolytic decomposition in protic media with NO formation than its isostructural analog with the unsubstituted pyridylthiolate ligand. The maximum amount of NO generated by complex I in a 1% aqueous solution of dimethyl sulfoxide at T = 25°C and pH 7.0 is 7.4 nmoles and increases twofold with an increase in the acidity of the medium (to pH 6.5) or temperature (37°C).