Reaction Of Tri Research Articles

PREPARATION AND CHARACTERIZATION OF PERFLUOROETHYLSUBSTITUTED ALKYLAMMONIUM OLIGOFLUOROPHOSPHATES

Mono-, di-, triperfluoroethyl substituted fluorophosphate anions are building blocks in the molecular design of salts with onium cations, and are used to increase hydrophobicity, modify surfactant properties and electrical conductivity. The work proposes methods for the synthesis of superacid H+[PF3(C2F5)3]- by the reaction of tri(pentafluoroethyl)difluorophosphorane with a solution of hydrofluoric acid, as well as superacids H+[PF4(C2F5)2]- and H+[PF5C2F5]- by step-by-step removal of the pentafluoroethyl substituent by hydrolysis with subsequent treatment with HF solution. Ionic compounds were synthesized by metathesis of anions at 0 °C from the corresponding quaternary ammonium chloride based on the obtained superacids. The article presents NR4FAP-class ionic compounds with the tributylmethylammonium (TBMA) cation of the general formula [(C4H9)3NCH3]+[PF6-n(C2F5)n]-, where n = 1, 2, 3. The square bipyramidal structure of the three studied anions was confirmed by nuclear magnetic resonance (NMR) spectroscopy and X-ray diffraction (XRD) data. The study shows, the synthesized compounds are characterized by extremely low vapor pressure up to 300 °C, a wide range of the liquid state with a width of up to 310 K by the methods of differential scanning calorimetry (DSC) and synchronous thermal analysis (STA). Melting temperatures and enthalpies were determined. The TBMA salts belong to ionic liquids (IL's), including one type liquid at room temperature (RT-IL). The general patterns of compounds decomposition were analyzed by the analysis of evolved gases (STA-EGA); it was shown that in all cases, the decomposition of the studied ionic liquids begins with the destruction of the anion. The electrical resistance of a pure ionic liquid at room temperature was studied. The described characteristics of perfluoroethylsubstituted alkyl ammonium oligofluorophosphates open up prospects for their use as electro conducting and antistatic additives for petrochemicals, fuels and polymers. For citation: Mokrushin I.G., Pinegina O.A., Krasnovskikh M.P., Dmitriev M.V., Markin I.V., Kozen A.L. Preparation and characterization of perfluoroethylsubstituted alkylammonium oligofluorophosphates. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 5. P. 54-61. DOI: 10.6060/ivkkt.20246705.6916.

2,3,4,5-Tetraiodopyrrole as a building block for halogen bonding: Formation of supramolecular hybrids with organic iodide salts in solid state

Reactions of tri(n-propyl)ammonium (1) or 1,3,5-trimethylpyridinium (2) iodides with 2,3,4,5-tetraiodopyrrole (TIP) results in formation of hybrids CatI•TIP•xEtOH (X = 0.5 (1) and 0.33 (2), respectively) which feature strong halogen bonding (XB) between I atoms of TIP and iodide anions. DFT calculations reveal that XB energies are up to 4.3 kcal/mol.

A porous Cd-based metal-organic framework for sensitive and selective detection of aspartic acid/Ag+ in aqueous medium

The development of a fast and stable luminescence detection method is of great significance to people's health and the protection of the ecological environment. In this work, a porous three-dimensional (3D) Cd-based metal-organic framework (MOF1) has been synthesized by the reaction of tri(p-carboxyphenyl)phosphane oxide (H3L) and 1,4-bis(pyrid-4-yl)benzene (1,4-bpb) with Cd2+ ions based on the mixed-ligand strategy, and characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and scanning electron microscope (SEM), etc. The luminescence experiments of MOF1 for amino acids and cations showed that MOF1 has highly sensitive and selective recognition for aspartic acid/Ag+ in aqueous medium. Meanwhile, the recognition mechanism of MOF1 for aspartic acid/Ag+ was analyzed by a series of experiments, the results indicate that the energy gap between HOMO energy values of H3L and aspartic acid/Ag+ is recognition impetus of MOF1 for aspartic acid by enhancement luminescence and for Ag+ by luminescence quenching, the sensing processes of MOF1 for aspartic acid and Ag+ ions are dynamic and static respectively by fluorescence lifetimes. Furthermore, the cycle and anti-interference experiments indicate that MOF1 has good luminescence stability and high sensing selectivity for aspartic acid and Ag+. The above results indicate that MOF1 has potential applications in recognizing aspartic acid and Ag+ in aqueous medium.

Ionic liquids: green solvents and reactive compounds? Reaction of tri-n-butylmethylphosphonium dimethylphosphate with elemental sulfur

Abstract The opening of the S8 ring with the formation of linear sulfur oligomers in the presence of tri-n-butylmethylphosphonium dimethylphosphate is shown. The reaction products are separated and characterized with 1H, 13C, 31P, 17O NMR spectroscopy, HD-MS, MALDI spectroscopy and XRD. It is shown that dimethylphosphate-anion is active in the reaction, and the addition of sulfur atoms occurs via the oxygen atom of dimethylphosphate-anion. It is found that a mixture of products is formed, which differ in the number of sulfur atoms in the chain. The assumptions were made about the mechanism of interaction of sulfur with tri-n-butylmethylphosphonium dimethylphosphate.

Triarylbismuth Dicarboxylates Ar3Bi[OC(O)R]2, Ar = p-Tol, R = CH2Cl; Ar = Ph, R = C6H4OMe-2, CH=CHPh

Triarylbismuth dicarboxylates Ar3Bi[OC(O)R]2, Ar = p-Tol, R = CH2Cl (I); Ar = Ph, R = C6H4OMe-2 (II), CH=CHPh (III) have been synthesized by the reactions of tri(para-tolyl)bismuth with monochloroacetic acid and triphenylbismuth with 2-methoxybenzoic and cinnamic acids in methyl-tert-butyl ether in the presence of tert-butyl hydroperoxide with a high yield. The Bi atoms in complexes I–III have a distorted trigonal bipyramidal coordination with carboxylate ligands in axial positions (OBiO angles, 171.06(6)° (I), 170.46(12)° (II), 175.39(8)° (III)). The Sb-O and Sb-C bond lengths are 2.283(2), 2.288(2) A and 2.185(2)–2.199(2) A (I), 2.265(7), 2.268(7) A and 2.194(7)–2.218(8) A (II), and 2.310(2), 2.310(2) A and 2.200(2)–2.210(3) A (III). Molecules of complexes I–III have intramolecular contacts between the Bi atom and the O atoms of carbonyl groups: the Bi⋯O(=C) distances are 2.990(2), 2.985(3) A (I), 2.753(8), 2.739(8) A (II), and 2.688(2) A (III). The structural organization in crystals of complexes I–III is caused by weak inter-molecular hydrogen bonds H⋯O of 2.61–2.65 A (I), 2.47–2.50 A (II), and 2.56 A (III).

4-Нитрофенилацетаты тетра- и три-(пара-толил)сурьмы. Синтез и особенности строения

The interaction of penta( para -tolyl)antimony with 4-nitrophenylacetic acid in toluene have synthesized tetra( para -tolyl)antimony 4-nitrophenylacetate ( 1 ). The reaction of tri( para -tolyl)­antimony with tert -butyl hydroperoxide and 4-nitrophenylacetic acid in diethyl ether leads to the formation of tri( para -tolyl)antimony bis (4-nitrophenylacetate) ( 1 ). The X-ray diffraction pattern has been obtained at 293 K on an automatic diffractometer D8 Quest Bruker (Mo K α -radiation, λ = 0.71073 Å, graphite monochromator) of crystals 1 [C 72 H 68 N 2 O 8 Sb 2 , M 1332.78, the triclinic syngony, the symmetry group P –1; cell parameters: a 12.08(3), b 16.46(3), c 17.79(3) Å, α = 107.61(7) degrees, β = 97.20(10) degrees, γ = 101.94(9) degrees; V = 3229(11) Å 3 ; the crystal size is 0.51×0.24×0.17 mm; intervals of reflection indexes are –10 ≤ h ≤ 10, –14 ≤ k ≤ 14, –15 ≤ l ≤ 15; total reflections 14622; independent reflections 4546; R int 0.0697; GOOF 1.072; R 1 = 0.0585, wR 2 = 0.1688; residual electron density 0.75/–0.85 e/Å 3 ] and 2 [C 37 H 33 O 8 N 2 Sb, M 755.40, the monoclinic syngony, the symmetry group P2 1 /n ; cell parameters: a 9.271(2), b 28.413(7), c 13.604(3) Å, α = 90.00 degrees, β = 105.876(2) degrees, γ = 90.00 degrees; V = 3425.5(13) Å 3 ; the crystal size is 0.95×0.58×0.34 mm; intervals of reflection indexes are –16 ≤ h ≤ 16, –50 ≤ k ≤ 50, –24 ≤ l ≤ 24; total reflections 125931; independent reflections 20517; R int 0.0450; GOOF 1.114; R 1 = 0.0511, wR 2 = 0.0993; residual electron density 0.70/–0.97 e/Å 3 ] the antimony atoms have distorted trigonal-bipyramidal coordination. The axial angles of OSbC and OSbO are 177.9 (5)°, 177.9 (5) ° ( 1 ) and 177.27(5)° ( 2 ); the sum of the angles of CSbC in the equatorial plane is 356.9°, 357.6° ( 1 ), 359.79° ( 2 ). The Sb–O and Sb–C bond lengths are 2.1443(15)–2.269(10) Å and 2.098(15)–2.170(14) Å. The structural organization of crystals 1 and 2 is controlled by intermolecular bonds O···H (2.46–2.67 Å). Complete tables of coordinates of atoms, bond lengths and valence angles for structures 1 and 2 are deposited at the Cambridge Structural Data Bank (no. 1819287, 1819295; deposit@ccdc.cam.ac.uk; http: //www.ccdc. Cam.ac.uk).

Facile reactions of gold(i) complexes with tri(tert-butyl)azadiboriridine.

Direct structural evidence for group 11 metal-mediated B-B bond activation was obtained from reactions of tri(tert-butyl)azadiboriridine (1) with AuCl(L) complexes. The AuCl(SMe2) reaction afforded [η2-B,B-B(tBu)N(tBu)B(tBu)]AuCl (2) by ligand displacement. More donating phosphines as co-ligands led to B-B bond cleavage accompanied by either halide or L migration to form boron-gold complexes 3 (L = PPh3) and 4 (L = PMe3). A similar product 5, which is isostructural to 4, was obtained by the addition of dimethylaminopyridine (DMAP) to 2-4. Complexes 2-5 constitute rare examples of metal complexes bearing two Lewis acidic centres. The effect of the boryl ligand was demonstrated in the formation of a gold(i) complex 6 bearing a 5-membered heterocycle from 3 and tert-butylisonitrile. Plausible reaction mechanisms that led to these complexes and their bonding situation were explored computationally at the DFT level.

Synthesis and structure of tri(o-tolyl) antimony dioximates

Tri(o-tolyl) antimony dioximates were synthesized by the reaction of tri(o-tolyl) antimony with 5-nitrofurfural and thiophen-2-carbaldehyde oximes in ether in the presence of hydrogen peroxide or tert-butylhydroperoxide (1: 2: 1 mol). Antimony atoms in the reaction products have distorted trigonal-bipyramidal coordination with the intramolecular distances Sb···N shorter than the sum of the van der Waals radii of Sb and N by ~1 A.

Reaction of Tri(2‐pyridyl)phosphine with Electron‐Deficient Alkynes in Water: Stereoselective Synthesis of Functionalized Pyridylvinylphosphine Oxides

AbstractThe reaction of tri(2‐pyridyl)phosphine with electron‐deficient alkynes in water proceeds under mild conditions (40–45 °C, without catalyst, 4–5 h) with liberation of pyridine to give (E)‐pyridylvinylphosphine oxides in 45–56 % yields, the only exception being the reaction with cyanophenylacetylene, which affords the corresponding vinylphosphine oxide of Z‐configuration in 40 % yield. The reaction is likely triggered by the zwitterion, the adduct of tri(2‐pyridyl)phosphine to the electrophilic acetylenes, the carbanionic center of which is then neutralized by a proton from water. The intermediate phosphonium hydroxide finally decomposes to the product.

Features of reactions of polyfluorinated ethyl 4-oxo-2-pnenyl-4H-chromene-3-carboxylates with N-nucleophiles

Ethyl 5,6,7,8-tetrafluoro-4-oxo-2-phenyl-4H-chromene-3-carboxylate in reactions with primary amines is characterized by a chromone-coumarin rearrangement affording 3-[amino(phenyl)methylene]-6,7,8-trifluoro-2H-chromene-2,4(3H)-diones, and ethyl 4-oxo-2-phenyl-5,6,7,8-tetrafluoro-4H-chromene-3-carboxylate characteristically adds the amine at the C2 site of the flavone furnishing 3-amino-3-phenyl-2-(2,3,4,5-tetrafluoro-6-hydroxybenzoyl)acrylates which depending on the substituent at the amino group are capable of intramolecular cyclization into 3-[(alkylamino)(phenyl)methylene]-5,6,7,8-tetrafluoro-2H-chromene-2,4(3H)-dione or in the case of benzylamine substituent, into ethyl 1-benzyl-5-hydroxy-4-oxo-2-phenyl-6,7,8-trifluoro-1,4-dihydroquinoline-3-carboxylate. The main process in the reaction of tri- and tetrafluoroflavones with secondary amine (1-methylpiperazine) is the nucleophilic substitution at the C7 of flavone. In the reaction with 1,2-phenylenediamine 3-[(2-aminophenyl)amino]-3-phenyl-2-(2,3,4,5-tetrafluoro-6-hydroxybenzoyl)acrylate was obtained from tetrafluoroflavone and 1H-benzimidazol-2-yl(3,4,5-trifluoro-2-hydroxyphenyl)methanone, from trifluoroflavone.

Design strategy for arranging an aromatic cyclic trimer into a tripodal molecule

Arranging an aromatic cyclic trimer into a tripodal molecule was achieved by the reaction of tri(bromomethyl)benzene with substituted benzimidazoles. The edge-to-face C–H⋯π interactions in the trimer stabilize the conformation of flexible molecules.

Oxidative addition reactions of tri(2-methylphenyl)antimony

Bis[μ-oxo-tri(2-methylphenyl)antimony] (I) was synthesized via oxidation of tri(2-methylphenyl)antimony by hydrogen peroxide in ether. In the presence of 2-hydroxy-5-bromobenzaldoxime or furfural oxime, the reaction between these reactants (in a 1: 1: 1 molar ratio, respectively) yields (μ-oxo)bis[2-hydroxy-5-bromobenzaldoximato-tri(2-methylphenyl)antimony] (II) or (μ-oxo)bis[furfural-oximatotri(2-methylphenyl)antimony] (III). The structures of compounds I–III was determined by X-ray diffraction. In the centrosymmetric dimeric complex I, the Sb atom has a distorted trigonal-bipyramidal coordination with oxygen atoms in equatorial and axial positions. In II and III, the axial positions are occupied by the bridge oxygen atom and the oxygen atom of the oxime ligand. Bond length values are as follows: Sb-C 2.137(3)–2.183(3), 2.116(7)–2.131(7), and 2.105(5)–2.126(6)A; Sb-O 1.934(2), 2.077(2), 1.973(4)–2.151(4), and 1.9706(3)–2.112(6) A for I, II, and III, respectively. Intramolecular contacts Sb...N (2.953(8), 3.002(9), and 2.951(8) II and III.

Boron-based electrolyte solutions with wide electrochemical windows for rechargeable magnesium batteries

Recently, we have developed a boron based electrolyte system with outstanding electrochemical performance, formed through the reaction of tri(3,5-dimethylphenyl)borane (Mes3B) and PhMgCl in THF, for rechargeable magnesium batteries. In this paper, the main components and equilibria of the unique boron based electrolyte solutions are identified by NMR, single-crystal XRD, etc. The results prove that the solutions contain various magnesium species, such as Mg2Cl3+, MgCl+, Ph2Mg and the tetracoordinated boron anion [Mes3BPh]−. Fluorescence spectra and Raman spectroscopy analyses indicate that the high anodic stability (ca. 3.5 V vs. Mg reference electrode (RE)) of the Mes3B–(PhMgCl)2 electrolyte is attributed to the non-covalent interactions between the anion [Mes3BPh]− and Ph2Mg. Furthermore, the air sensitivity of the boron based electrolyte and its electrochemical stability on the different current collectors are studied. Finally, the reversible electrochemical process of Mg intercalation into a Mo6S8 cathode confirms that the boron based electrolyte could be practically used in rechargeable Mg battery systems.

Electrochemical performance of novel electrolyte solutions based on organoboron magnesium salts

A novel boron based electrolyte system based on reaction of tri(3,5-dimethylphenyl)borane (Mes3B) and PhMgCl in THF solution is proposed for the potential application in rechargeable magnesium battery. The optimized composition of Mes3B-(PhMgCl)2/THF electrolyte solution presents high ionic conductivity(ca. 2×10−3S/cm in 0.5M solution) at room temperature, excellent Mg deposition reversibility as well as the highest anodic potential to date (3.5V vs. Mg RE). The initial results indicate that the high-performance of the Mes3B–(PhMgCl)2 electrolyte might be attributed to non-covalent interactions arising from the excess amount of Grignard reagent PhMgCl. This study opens the door to the development of boron based electrolyte chemistry for high-energy rechargeable Mg batteries.

Reactivity of tri(2-furyl)phosphine (PFu3) with [Mn2(CO)10–n(NCMe)n] (n = 0–2): X-ray Structure of mer-[Mn(CO)3(η1-C4H3O)(PFu3)2

Reaction of tri(2-furyl)phosphine (PFu3) with [Mn2(CO)10−n(NCMe)n] (n=1, 2) at room temperature furnished the substituted complexes [Mn2(CO)10−n(PFu3)n] (1–2). Direct reaction between Mn2(CO)10 and PFu3 in refluxing toluene also afforded 2 together with mer-[Mn(CO)3(η1-C4H3O)(PFu3)2] (3) resulting from phosphorus–carbon bond cleavage of the phosphine. All three new complexes have been characterized by spectroscopic data together with single crystal X-ray diffraction studies for 3.

Synthesis and structure of tri-m-tolylantimony bis(1-adamantanecarboxylate)

Tri(m-tolyl)antimony bis(1-adamantanecarboxylate) (3-MeC6H4)3Sb[OC(O)C10H15]2 has been synthesized with a yield of 90.0% by the reaction of tri(m-tolyl)antimony with 1-adamantanecarboxylic acid in the presence of hydrogen peroxide in ether. According to X-ray diffraction analysis data, the antimony atom has a distorted trigonal-bipyramidal coordination with the axially positioned oxygen atoms of carboxyl groups. The axial OSbO angle is 173.1(2)°; the equatorial CSbC angles are 112.0(1)°, 112.0(1)°, and 136.0(3)°; the Sb-O distance is 2.109(3)A; the Sb-C distances are 2.103(5), 2.103(5), and 2.121(7) A; intramolecular Sb…O(=C) contacts are 3.069(5) A.

Confirmation of Bridging N-Indolides in 3-Methylindole and Di- and Tri(3-methylindolyl)methane Complexes of Dimethyl-, Diethyl-, and Diisobutylaluminum

Reactions of 3-methylindole with one equivalent of R3Al produce the N-indolide-bridged dimers [(3-CH3C8H5N)AlR2]2 (R = Me (3a), Et (3b), iBu (3c)). NMR spectroscopy (1H, 13C) demonstrates that compounds 3a, 3b, and 3c each exist in solution as a mixture of interconverting syn and anti isomers. Reactions of di(3-methylindolyl)methane or tri(3-methylindolyl)methane with one equivalent of Me3Al or Et3Al similarly produce the N-indolide-bridged compounds [(Ph)HC(3-CH3C8H4NAlR2)2] (R = Me (4)) or [HC(3-CH3C8H4NAlR2)3] (R = Me (5a), Et (5b)), respectively. Reaction of tri(3-methyl-2-indolyl)methane with one equivalent of iBu3Al yielded the N-indolide-bridged compound [HC(3-CH3C8H4NAliBu2)2(3-CH3C8H4NAl(H)iBu)] (6), apparently the result of β-hydrogen elimination of isobutene from one isobutyl group per complex. The molecular structures of compounds 3a, 4, and 5a were determined by X-ray crystallography. Crystallographic data confirmed the presence of μ2-η1:η1-N-3-methylindolide groups in each compound, the first examples of bridging N-indolide groups in compounds of the group 13 elements.

Reaction of tri(2-furyl)phosphine with triosmium clusters: C–H and P–C activation to afford furyne and phosphinidene ligands

Addition of tri(2-furyl)phosphine, PFu 3, to [Os 3(CO) 10(μ-H) 2] at room temperature gives [HOs 3(CO) 10(PFu 3)(μ-H)] ( 1), while in refluxing toluene the same reactants afford [Os 3(CO) 9{μ 3-PFu 2(C 4H 2O)}(μ-H)] ( 2) resulting from orthometallatation of a furyl ring. Reaction of PFu 3 with [Os 3(CO) 10− n (NCMe) n ] ( n = 0, 1, 2) affords the substituted clusters [Os 3(CO) 12− n (PFu 3) n ] ( n = 1–3) ( 3–5), the phosphine ligands occupying equatorial position in all cases. Heating [Os 3(CO) 11(PFu 3)] ( 3) in refluxing octane gives [Os 3(CO) 9(μ 3-PFu)(μ 3-η 2-C 4H 2O)] ( 6) which results from both carbon–hydrogen and carbon–phosphorus bond activation and contains both μ 3-η 2-furyne and furylphosphinidene ligands. All new clusters have been characterized by spectroscopic methods together with single crystal X-ray diffraction for 2, 3 and 6.

Activation of tri(2-furyl)phosphine at a dirhenium centre: Formation of phosphido-bridged dirhenium complexes

Reaction of tri(2-furyl)phosphine (PFu 3) with [Re 2(CO) 10− n (NCMe) n ] ( n = 1, 2) at 40 °C gave the substituted complexes [Re 2(CO) 10− n (PFu 3) n ] ( 1 and 2), the phosphines occupying axial position in all cases. Heating [Re 2(CO) 10] and PFu 3 in refluxing xylene also gives 1 and 2 together with four phosphido-bridged complexes; [Re 2(CO) 8− n (PFu 3) n (μ-PFu 2)(μ-H)] ( n = 0, 1, 2) ( 3– 5) and [Re 2(CO) 6(PFu 3) 2(μ-PFu 2)(μ-Cl)] ( 6) resulting from phosphorus–carbon bond cleavage. A series of separate thermolysis experiments has allowed a detailed reaction pathway to be unambiguously established. A similar reaction between [Re 2(CO) 10] and PFu 3 in refluxing chlorobenzene furnishes four complexes which include 1, 2, 6 and the new binuclear complex [Re 2(CO) 6(η 1-C 4H 3O) 2(μ-PFu 2) 2] ( 7). All new complexes have been characterized by a combination of spectroscopic data and single crystal X-ray diffraction studies.

Identification of Aliphatic and Aromatic Tertiary N-Oxide Functionalities in Protonated Analytes via Ion/Molecule and Dissociation Reactions in an FT-ICR Mass Spectrometer

A mass spectrometric method is presented for the identification of compounds that contain the aliphatic or aromatic N-oxide functional group. This method utilizes gas-phase ion/molecule reactions of tri(dimethylamino)borane (TDMAB), which rapidly derivatizes protonated aliphatic and aromatic tertiary N-oxides, amides, and some amines via loss of dimethylamine in a Fourier transform ion cyclotron resonance mass spectrometer. The mechanism involves proton transfer from the protonated analyte to the borane, followed by addition of the analyte to the boron center and elimination of dimethylamine. The derivatized analytes are readily identified on the basis of their m/z value which is 98 Th (thomson) greater than that of the protonated analyte, and the characteristic boron isotope patterns. SORI-CAD of the product ions (adduct-(CH3)2NH) yields different fragment ions for aliphatic tertiary N-oxides, aromatic tertiary N-oxides, amides, and pyridines. Therefore, these analytes can be identified based on their characteristic fragment ions. This method was tested by examining two drug samples, Olanzapine and Olanzapine-4' N-oxide.