Interaction Of Tris Research Articles

Ligand-assisted excitation of Eu(III) during interaction of Eu(FOD)3 with xenon difluoride in acetonitrile solution

The interaction of tris(1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionato)europium(III), (Eu(FOD)3), with xenon difluoride in acetonitrile solution was found to be accompanied by chemiluminescence (CL). The kinetic curve of CL at a ratio of reagents Eu3+/XeF2 of 1:2 has a complex form; an initial rapid decrease is replaced by an increase in CL intensity, the maximum of which is reached approximately 10 min after the start of the reaction. Next, an exponential decay of the CL intensity is observed over several tens of minutes. The CL spectrum is located in the wavelength range 400–750 nm and corresponds to the emission of an electronically excited europium (III) ion coordinated with FOD and fluoride ion. Spectral methods were used to identify the reaction products – europium (III) fluoride in the sediment and oxygen difluoride in the gas phase. A mechanism for chemiexcitation of europium(III) has been proposed, including: 1) acceptance of fluorine anion from the XeF2 molecule by europium ion with the formation of active intermediate XeF+; 2) oxidative fluorination of the ligand, which is initiated by the interaction of oxygen atom of the FOD ligand with XeF+ cation and ends with the formation of oxygen difluoride and the electronically excited product P*, presumably a fluorinated ketone; 3) non-radiative transfer of excitation energy from P* to the europium ion within its coordination sphere, followed by its radiative deactivation.

Синтез и строение производных трис(4-трифторметил-фенил)сурьмы

Interaction of tris(4-trifluoromethylphenyl)antimony (1) with copper(II) chloride and copper(II) bromide in acetone has been used to synthesize tris(4-trifluoromethylphenyl)antimony dichloride (2) and dibromide (3), yielding 85 % and 92 %, respectively. Oxidation of 1 by tert-butyl hydroperoxide in the presence of 2,5-difluorobenzoic acid (mole ratio 1:1:2) in ether is accompanied by the formation of tris(4-trifluoromethylphenyl)antimony bis(2,5-difluorobenzoate) (4), yielding 81%. Compounds 1–4 have been identified by IR spectroscopy and X-ray diffraction analysis. According to the X-ray analysis data, obtained on an automatic D8 Quest Bruker diffractometer (Mo K-radiation, λ = 0.71073 Å, graphite monochromator) at 293 K, for crystals 1 [C21H12F9Sb, M 557.06, symmetry group Р–1; cell parameters: a = 10.858(13) Å, b =11.072(13) Å, c = 11.432(18) Å, α = 104.91(7) degrees, β = 113.61(5) degrees, γ = 106.89(5) degrees; V = 1090(3) Å3; the crystal size is 0.34  0.33  0.3 mm; intervals of reflection indexes are 14  h  14, 15  k  15, 15  l  15; total reflections 40268; independent reflections 5862; Rint 0,0477; GOOF 1.049; R1 = 0.0533, wR2 = 0.1427; residual electron density 1.16/1.04 e/Å3], 2 [C21H12F9Cl2Sb, M 627.98, symmetry group Р–1; cell parameters: a = 7.920(4) Å, b = 14.732(7) Å, c = 21.759(13) Å, α = 75.31(2) degrees, β = 86.12(3) degrees, γ = 76.10(2) degrees; V = 2384(2) Å3; the crystal size is 0.650.150.11 mm; intervals of reflection indexes are 11  h  11, 21  k  22, 32  l  32; total reflections 138621; independent reflections 12076; Rint 0.0553; GOOF 1.109; R1 = 0.0429, wR2 = 0.0960; residual electron density 1.28/1.06 e/Å3], 3 [C27H18Br2F9Sb, M 794.98, symmetry group Р–1; cell parameters: a = 9.129(8) Å, b = 12.120(8) Å, c = 14.454(14) Å, α = 76.41(3) degrees, β = 85.93(5) degrees, γ = 68.69(3) degrees; V = 1448(2) Å3; the crystal size is 0.490.490.31 mm; intervals of reflection indexes are 12  h  12, 16  k  16, 19  l  19; total reflections 64492; independent reflections 7337; Rint 0.0545; GOOF 1.014; R1 = 0.0366, wR2 = 0.0817; residual electron density 0.68/0.61 e/Å3], and 4 [C35H18F13O4Sb, M 871.27, symmetry group Р–1; cell parameters: a = 11.575(14) Å, b = 12.017(17) Å, c = 15.041(16) Å, α = 76.33(5) degrees,β = 69.62(5) degrees, γ = 64.04(6) degrees; V = 1755(4) Å3; the crystal size is 0.31  0.12  0.11 mm; intervals of reflection indexes are 15  h  14, 15  k  15, 19  l  19; total reflections 44416; independent reflections 8033; Rint 0.0393; GOOF 1.072; R1 = 0.0326,wR2 = 0.0798; residual electron density 1,03/0,57 e/Å3], the antimony atoms in 1 have a trigonal pyramidal coordination, in 24 they have a trigonal bipyramidal coordination with electronegative ligands in axial positions. The Sb–C bond lengths in 1 are 2.155(5), 2.164(6), and 2.170(5) Å, the CSbC bond angles are 95.04(18), 95.70(17), and 97.20(18) degrees, which is less than the value of the tetrahedral angle; this is explained by the presence of a lone electron pair on the antimony atom. The C–F bond lengths vary in the range of 1.143(12)–1.334(11) Å. Crystals 2 consist of two types of crystallographically independent molecules, the geometrical parameters of which differ slightly from each other. Compound 3 is (4-CF3C6H4)3SbBr2 ∙ PhH solvate. In crystal 4, antimony atoms are coordinated by the oxygen atoms of bidentate carboxylate ligands (the Sb–O and Sb∙∙∙O=C distances are 2.120(3), 2.144(3), and 2.829(5), 2.911(6) Å, respectively).

New Aspects of Ruthenium-Mediated Polyhedral Contraction of Monocarbollides

It has been shown that the interaction of tris(triphenylphosphine)ruthenium dichloride RuCl2(PPh3)3 (1) with 10-vertex monocarborane [6-Ph-nido-6-CB9H11]−[Et4N]+ (2) under mild thermolysis conditions is not selective due to the undesired coordination of ruthenium to a phenyl substituent in the carborane and phosphine ligands, giving the series of new classical and non-classical metallacarborane complexes. In contrast, the reaction of 1 and monocarborane [arachno-6-CB9H14]−[Et4N]+ (3) proceeds more selectively with the formation of the only one product, a isocloso-structured metallacarborane. The structures of two ruthenacarboranes were resolved by X-ray diffraction.

Synthesis, structure and properties of tris(hydroxymethyl)aminomethane complexes with biogenic metal salts

New coordination compounds - analogues of hydrometallatranes, characterized by FT-IR spectroscopy, mass spectrometry and elemental analysis, were synthesized by the interaction of tris(hydroxymethyl)aminomethane (TRIS) with Cu(II), Co(II), Ni(II) and Zn(II) salts of carboxylic acids. The crystal structure of TRIS complex with Cu(II) cinnamate was determined by X-ray diffraction. The structural parameters and gap energy for this complex have been calculated by the DFT method. The thermal analysis data for new TRIS complexes are presented. The effect of some TRIS hydrometallatranes, as well as TEA and TPA hydrometallatranes on the growth of corrosion-aggressive thionic bacteria was studied.

Interactions of Tris with rutile surfaces and consequences for in vitro bioactivity testing

Tris(hydroxymethyl)aminomethane (Tris) has been used as the buffer in bioactivity testing for over two decades and has become a standard choice for the scientific community. While it is believed to be non-interacting, the extent of its interactions with titanium oxide surfaces has not been systematically studied. Here, we use experimental (zeta potential measurements) and computational (molecular dynamics) approaches to evaluate the interaction of Tris with a rutile surface and how it affects the adsorption of other molecules relevant in biomedical in vitro testing. We show that the interaction of Tris with the rutile surface is strong and significantly affects the interaction of other organic residues with the surface. These strong interactions are compounded by the Tris concentration in the in vitro testing protocol, which is much higher compared to other components. Our findings indicate that the kinetics observed in in vitro tests will be strongly influenced by the presence of Tris as a buffering agent when compared to the natural CO2 buffer in blood. These results reveal that considering the so-far neglected active role of Tris in in vitro testing is critically needed and that in vitro protocols using CO2 partial pressure as the buffering agent should yield more reliable results.

Spectroscopic investigation of the interaction between crystal-violet and sodium dodecanoylsarcosinate

ABSTRACT The interaction of Tris(4-(dimethylamino)phenyl)methylium chloride (crystal violet (CV)) – a triphenylmethane dye with sodium dodecanoylsarcosinate – an amino acid-based anionic surfactant has been studied with a view to investigate the effect of the surfactant on the spectral behaviours of the dye. The dye–surfactant interaction was studied spectrophotometrically in aqueous solutions, and the dye was found to strongly interact electrostatically and formed ion-pair complex with the anionic surfactant at the pre-micellar surfactant concentrations. This is evidenced from the marked changes in the spectral behaviour of the dye in the presence of the surfactant. The complex ion-pair appeared to self-aggregate at a critical aggregate concentration of 2.50 mM. At and above the critical micelle concentration (CMC) of the pure surfactant, the dye became completely solubilised in the micelle. The extent of dye–surfactant complex ion-pair formation in the pre-micellar region and the dye–micelle-binding constants were determined from the Rose–Drago equation.

Interaction of Tris with DNA molecules and carboxylic groups on self-assembled monolayers of alkanethiols measured with surface plasmon resonance

Functional materials employing organic coatings on inorganic substrates are perceived as potential platforms for applications in a variety of fields. Therefore, the investigation of interactions of such systems with the microenvironment has become an important research direction in surface science. Herein, we study the interaction of one of the buffers most commonly used in biological studies, Tris buffer, with self-assembled monolayers (SAMs) of alkanethiols and short DNAs using a surface plasmon resonance (SPR) biosensor. We show that the interaction between Tris and carboxylic groups of SAMs is a complex multiphasic process. We demonstrate that Tris base binds to the protonated carboxylic groups. When those groups become deprotonated, Tris base dissociates and Tris acid is attracted, which results in the formation of a diffuse layer over the charged surface. In addition, we show that the interaction of Tris with the immobilized DNA molecules biases the determination of surface concentrations of the immobilized DNA molecules and thus also the determination of hybridization efficiencies.

Синтез и строение бис(2,5-диметилбензолсульфоната) и бис(дибромфторацетата) трис(3-фторфенил)сурьмы

The interaction of tris(3-fluorophenyl)antimony with 2,5-dimethylbenzenesulfonic or dibromofluoroacetic acid in diethyl ether in the presence of tert-butyl hydroperoxide has synthe-sized tris(3-fluorophenyl)antimony bis(2,5-dimethylbenzenesulfonate) (1) and tris(3-fluorophenyl)antimony bis(dibromofluoroacetate) (2). The X-ray diffraction pattern has been obtained at 293 K on an automatic diffractometer D8 Quest Bruker (MoKα-radiation, λ = 0.71073 Å, graphite monochromator) for crystal 1 [C34H30F2O6S2Sb, M 777.45, the triclinic syngony, the symmetry group P–1; cell parameters: a 10.634(18) Å, b 11.38(2) Å, c 14.31(3) Å, α = 90.51(8) degrees, β = 90.35(11) degrees, γ = 112.79(5) degrees; V = 1596(5) Å3; the crystal size is 0.5×0.48×0.17 mm; intervals of reflection indexes are –15 ≤ h ≤ 14, –15 ≤ k ≤ 15, –19 ≤ l ≤ 19; total reflections 30473; independent reflections 8318; Rint 0.0920; GOOF 1.894; R1 = 0.1699, wR2 = 0.4237; residual electron density 6.78/–5.48 e/Å3] and crystal 2 [C22H12O4F7SbBr2, M 754.89, the triclinic syngony, the symmetry group P–1; cell parameters: a 8.98(3) Å, b 10.41(2) Å, c 14.92(3) Å, α = 90.77(7) degrees, β = 90.73(9) degrees, γ = 113.95(10) degrees; V = 1275(5) Å3; the crystal size is 0.65 × 0.32 × 0.14 mm; intervals of reflection indexes are –13 ≤ h ≤ 13, –15 ≤ k ≤ 14, –21 ≤ l ≤ 21; total reflections 61066; independent reflections 8511; Rint 0.0863; GOOF 1.983; R1 = 0.1529, wR2 = 0.4647; residual electron density 4.41/–3.48 e/Å3] the antimony atoms have a distorted trigonal-bipyramidal coordination. The axial OSbO angles are 178.2(3) (1) and 174.0(4) (2); the sum of the CSbC angles in the equatorial plane is 360. The Sb–O and Sb–C bond lengths are 2.108(9)–2.131(12) Å and 2.090(14)– 2.21(3) Å. The structural organization of crystals 1 and 2 is controlled by intermolecular bonds O···H 2.53–2.70 Å (1) and 2.57–2.60 Å (2), F•••H 2.46–2.59 Å (1) and Br•••H 3.02 Å (2). In 2 the short contacts C··· F have been observed between the aryl ligands of neighboring molecules 3.079 and 3.085 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. 2055553, 2055764; depos-it@ccdc.cam.ac.uk; http: //www.ccdc.cam.ac.uk).

Исследование строения дикарбоксилатов трис(4-фторфенил)сурьмы (4-FC6H4)3Sb[OC(O)R]2 (R = C6H3F2-2,3, C6H3(NO2)2-3,5, C6H4OMe-2, CF2Br, CH=CHPh, CH3, C≡CH)

The interaction of tris(4-fluorophenyl)antimony with 2,3-difluorobenzoic acid, as well as with 3,5-dinitrobenzoic, 2-methoxybenzoic, bromodifluoroacetic, cinnamic, formic, and propionic acids in the presence of tert-butyl hydroperoxide (1:2:1 mol.) in ether at ambient temperature has given tris(4-fluorophenyl)antimony dicarboxylates (4-FC6H4)3Sb[OC(O)R]2, where R = C6H3F2-2,3 (1), C6H3(NO2)2-3,5 (2), C6H4OMe-2 (3), CF2Br (4), CH=CHPh (5), CH3 (6), и C≡CH (7). The IR spectra of compounds 17, recorded on a Shimadzu IRAffinity-1S Fourier transform IR spectrometer, in a KBr pellet within the 4000–400 cm–1 interval, contain absorption bands of carbonyl groups, which are shifted to the low-frequency vibration region in comparison with the IR spectra of the initial acids. According to the X-ray diffraction data obtained on a Bruker D8 QUEST diffractometer, compound 1 has the following crystallographic parameters of the unit cell: space group P-1, a = 9.034(4), b = 11.351(8), c = 14.814(9) Å, α = 70.11(3)°, β = 88.60(2)°, γ = 87.03(2)°, V = 1426(15) Å3, ρcalc = 1.679 g/cm3, Z = 2. The antimony atom in 1 has a distorted trigonal-bipyramidal coordination with carboxylate ligands in axial positions. The OSbO axial angle is 176.95 (6)°. The lengths of the Sb−O and Sb−C bonds are equal to 2.135(2), 2.121(2) and 2.113(3)–2.116 (3) Å. The Sb•••O=C distances are 3.040(2), 2.861 (3) Å, that is, less than the sum of the van der Waals radii of antimony and oxygen (3.70 Å). The antimony atom departs from the equatorial plane [C3] by 0.038 Å. Complete tables of atom coordinates, bond lengths and valence angles are deposited at the Cambridge Crystallographic Data Center (№ 2051716; deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk/data_request/cif).

Реакция окислительного присоединения трис(2-метокси-5-хлорфенил)сурьмы с трифторпропионовой кислотой

The interaction of tris(2-methoxy-5-chlorophenyl)antimony with 3,3,3–trifluoropropionic acid in the presence of hydrogen peroxide (1:2:1 mol) in ether proceeds according to the oxidative addition reaction scheme with the formation of bis(3,3,3-trifluoropropionyl)tris(2-methoxy-5-chlorophenyl)antimony [(MeO-2)(Cl-5)C6H3]Sb[OC(O)CH2F3]2. The IR spectra of compound 2, recorded on a Shimadzu IRAffinity-1S Fourier transform IR spectrometer in a KBr pellet in the region of 4000–400 cm–1, contain absorption bands of carbonyl groups, which are shifted to the low-frequency vibration region in comparison with the IR spectra of the initial acids. According to the X-ray diffraction data obtained on a Bruker D8 QUEST diffractometer, compound 1 has the following crystallographic parameters of the unit cell: crystal size 0.23×0.21×0.08 mm3, space group P21/n, а = 8.883(7), b = 21.184(15), c = 13.642(15) Å, α = 90.00°, β = 107.34(3)°, γ = 90.00°, V = 2451(4) Å3, ρcalc = 1.587 g/cm3, Z = 4; crystal 2 has the following crystallographic parameters of the unit cell: 0.3×0.25×0.08 mm3, P21/c, а = 12.00(5), b =16.81(7), c =16.30(9) Å, α =90.00°, β =108.3(3)°, γ =90.00°, V =3121(25) Å3, ρcalc = 1.704 g/cm3, Z = 4. The antimony atom in 2 has a distorted trigonal-bipyramidal coordination with carboxylate ligands in axial positions. The OSbО angles are 174.2(5)°, the sums of the СSbC angles in the equatorial plane are 360°, the axial Sb–O bonds equal 2.073(15), 2.092(15) Å, and the equatorial Sb–С bonds equal 2.05–2.13 Å, which is close to the sum of the covalent radii of the atoms. The intramolecular Sb∙∙∙OМе distances (3.035(3), 3.037(3), 2.992(4) Å (1), 3.03(2), 3.119(17), 3.147(19) Å (2)), as well as Sb∙∙∙OMe for compound 2 (3.232(19), 2.99(2) Å), are much smaller than the sum of the van der Waals radii of atoms.

Tris(hydroxymethyl)methyl ammonium salts of biologically active carboxylic acids. Synthesis, properties and crystal structure

Tris(hydroxymethyl)methyl ammonium salts, [C(CH2OH)3NH3]X, were obtained for the first time by the interaction of tris(hydroxymethyl)aminomethane (TRIS) with carboxylic acids (cinnamic, benzoic, salicylic, nicotinic, 2-methylphenoxyacetic, succinic, malonic, oxalic, malic and citric). The new compounds (1–15) were characterized by 1H NMR, 13C NMR, FT-IR, elemental analysis and thermal analysis methods. The crystal structures of the tris(hydroxymethyl)methyl ammonium hydrogen malonate, hydrogen succinate and 2-methylphenoxyacetate were determined by the single-crystal X-ray diffraction. The antimicrobial activity of some synthesized tris(hydroxymethyl)methyl ammonium salts against bacteria Escherichia coli, Staphylococcus aureus, Mycobacterium tuberculosis and fungi Candida albicans and Aspergillus niger has been investigated.

Synthesis and structure of a new complex of mercury(II) with an organoantimony ligand – tris(2,6-dimethoxyphenyl)stibane

The new heterometallic complex [HgI2(SbAr3)], Ar = 2,6-(MeО)2C6H3 has been obtained by the interaction of tris(2,6-dimethoxyphenyl)antimony with mercury(II) iodide. SbAr3 and [HgI2(SbAr3)] have been characterized using single crystal X-ray diffraction. Structures of them are compared. Elemental analysis, IR and NMR spectroscopies have also been used for characterization.

Синтез и строение хлоро¬(пентахлорфеноксида) трис(3-фторфенил)сурьмы (3-FC6H4)3SbCl(OC6Cl5)

Tris (3-fluorophenyl)antimony chloro(pentachlorophenoxide) ( 1 ) has been synthesized by the interaction of tris (3-fluorophenyl)antimony dichloride with tris (3-fluorophenyl)antimony bis (2,3,4,5,6-pentachlorophenoxide) (1:1 mol.) in benzene. The compound has been identified by IR spectroscopy and X-ray diffraction analysis. The absorption band of the stretching vibrations of the SbC 3 fragment at 432 cm –1 is observed in the IR spectrum of compound 1 . There is also an intensive absorption band at 1267 cm -1 , which characterizes stretching vibrations of the C-O bond. According to the X-ray diffraction analysis the coordination of the antimony atom is trigonal-bipyramidal with the chlorine and oxygen atoms in the axial positions [C 24 H 12 OCl 6 SbF 3 , M = 707.79; the triclinic system, space group P ; a 9.486(6), b 11.548(7); c 12.382(11) Å; α 73.61(2), β 87.03(3), γ 84.221(19) degrees; V 1294.2(17) Å 3 ; Z 2; µ 1.724 mm –1 ; F(000) 668.0; crystal size 0.26´0.22´0.11 mm; 2θ for data collection 5.7–62.22 degrees; index ranges −13 ≤ h ≤ 13, −16 ≤ k ≤ 16, −17 ≤ l ≤ 17; total reflections 79173; independent reflections 8254; R int 0.0560; variables 317, GOOF 1.021; R 1 = 0.0482; wR 2 = 0.1167; residual electron density 1.91/–0.56 e/Å 3 ]. The OSbCl axial angle in the molecule of compound 1 is 179.14(8)°. The sum of the CSbC angles in the equatorial plane is 360°, while the values of the individual angles vary in the interval 113.49 (15)°–126.16 (15)°. The Sb–O axial bond length is shorter than the Sb–C equatorial bond lengths and equals 2.092 (3) Å. This pattern is characteristic of most triaryl­antimony diaroxides. The formation of the compound 1 crystal structure is due to the formation of weak intermolecular contacts C–H×××Cl 2.89 Å and F×××Cl 3.08, 3.11 Å. Complete tables of coordinates of atoms, bond lengths and valence angles are deposited at the Cambridge Structural Data Bank (No. 1849662; deposit@ccdc.cam.ac.uk; http://www.ccdc. cam.ac.uk).

DFT Study on the Interaction of Tris(benzene-1,2-dithiolato)molybdenum Complex with Water. A Hydrolysis Mechanism Involving a Feasible Seven-Coordinate Aquomolybdenum Intermediate.

In the present work, the reactivity of the tris(benzene-1,2-dithiolato)molybdenum complex ([Mo(bdt)3]) toward water is studied by means of the density functional theory (DFT). DFT calculations were performed using the M06, B3P86, and B3PW91 hybrid functionals for comparison purposes. The M06 method was employed to elucidate the reaction pathway, relative stability of the intermediate products, nature of the Mo-S bond cleavage, and electronic structure of the involved molybdenum species. This functional was also used to study the transference of electrons from the molybdenum center toward the ligands. The reaction pathway confirms that [Mo(bdt)3] undergoes hydrolysis, yielding dihydroxo-bis(benzene-1,2-dithiolato)molybdenum complex ([Mo(OH)2(bdt)2]) and benzenedithiol. The reaction takes place through seven transition structures, one of them involving an aquo seven-coordinate molybdenum intermediate stabilized by a lone pair (LP) LPO→LPMo hyperconjugative interaction. This heptacoordinate species allows understanding of the observed oxygen atom exchange between water and tertiary phosphines mediated by these complexes. Calculations also show that [Mo(C2H4S2)3] and [Mo(OH)2(C2H4S2)2] have d2 and d0 electronic configuration, and hence an electron pair must be transferred during the course of the hydrolysis. The frontier molecular orbital (FMO) analysis concludes that the electron pair is transferred in the rupture of the second Mo-S bond, from the occupied donating Mo dx2-y2 orbital to the unoccupied C2H4(SH)2 S-C σ* ligand orbital. This result is supported by the bond dissociation energy calculations, which demonstrate that the neutral dissociation of the second Mo-S bond is energetically the more favorable.

Synthesis and structure of tris(4-fluorophenyl)antimony dicarboxylates

The interaction of tris(4-fluorophenyl)antimony with chloroacetic, 4-nitrophenylacetic, and benzoic acids in diethyl ether in the presence of tert-butyl hydroperoxide has yielded tris(4-fluorophenyl)antimony dicarboxylates, their Sb atoms bearing distorted trigonal bipyramid coordination with the carboxylate ligands in the axial positions. The intramolecular contacts between Sb atom and carbonyl O atom are formed in the molecules of the products. Their crystal packing is determined by weak intermolecular hydrogen bonds of the H···F and H···O=C types.

Synthesis, structure, and reactions of tris(4-fluorophenyl)antimony dibromide

The interaction of tris(4-fluorophenyl)antimony with copper(II) bromide in acetone has afforded tris(4-fluorophenyl)antimony dibromide; recrystallization of the product from ethanol has yielded the (4-FC6H4)3SbBr2·[(4-FC6H4)3SbBr]2O adduct. [(4-FC6H4)3SbCNS]2O oxide has been prepared from tris(4-fluorophenyl)antimony dibromide and potassium thiocyanate in aqueous-acetone solution. Antimony atoms in the molecules of the prepared compounds exhibited the distorted trigonal bipyramid coordination with the electron-accepting ligands in the axial positions.

NMR Spectroscopic Studies on the 1:1 Interaction of Tris(hydroxymethyl)phosphine with Cinnamic Acids

AbstractA 1:1 reaction of (HOCH2)3P with the cinnamic acids ArCH=CHCO2H (Ar = Ph, o‐ and p‐C6H4OH) in acetone at 60 °C affords a phosphobetaine of the type (HOCH2)3P+CH(Ar)CH2CO2– in 70–80 % yields; the products were characterized by 31P{1H}‐, 1H‐, and 13C{1H}‐NMR spectroscopy, and mass spectrometry. In methanol, the compounds decompose partially to a tertiary phosphine of the type (HOCH2)2PCH(Ar)CH2CO2H; the degree of decomposition decreases in the order Ar = o‐C6H4OH > p‐C6H4OH > C6H5. The 1:1 reaction of (HOCH2)3P with cinnamic acid in CD3OD generates (DOCH2)3P+CH(Ph)CH(D)CO2– and (DOCH2)2PCH(Ph)CH(D)CO2D, whereby addition of a deuteron to the α‐C atom is stereospecific and leads to (R,S)‐ and (S,R)‐stereoisomers.

Synthesis of aminomethylenediphosphonates and their derivatives containing PCNH2 fragments

Aminomethylenediphosphonic acids containing free amino group are of interest as promising ligands and biologically active substances with diverse properties [1]. We recently developed several convenient methods for the synthesis of N-substituted aminomethylenediphosphonates starting from Nsubstituted formamides and imines [2]. For the synthesis of new trimethylsilyl-containing aminomethylenediphosphonates and their derivatives with PCNH2 fragments we studied the interaction of tris(trimethylsilyl)phosphate with easily accessible hydrochlorides of substituted ethoxymethyleneimines A [3] in the presence of trimethylsilyl trifluoromethanesulfonate as a catalyst. Thus, substituted ethoxymethyleneimines hydrochlorides A reacted with an excess of tris(trimethylsilyl)phosphite in methylene chloride under mild conditions to form diphosphonates I–III with good yields. DOI: 10.1134/S1070363214030347

Interaction of Tris(2-aminoethyl)amine-based Ureas and Thiourea with Superoxide Anion and Peroxide Dianion through Multiple Hydrogen Bonding

Abstract Tris(2-aminoethyl)amine-based urea and thiourea derivatives interacted with a superoxide anion (O2−) and peroxide dianion (O22−): The redox potential of oxygen was positively shifted with the molecules through their multiple-hydrogen-bond donor ability.

Synthesis of p-tert-butylthiacalix[4]arenes functionalized with tris(2-aminoethyl)amine fragments at the lower rim and their interaction with model lipid membranes

New tetrasubstituted derivatives of thiacalix[4]arene functionalized with tris(2-aminoethyl)amine fragments at the lower rim in the cone, partial cone and 1,3-alternate conformations have been synthesized. It has been shown that during the interaction of tris(2-aminoethyl)amine with thiacalix[4]arenes in cone and partial cone conformation, the cyclic fragments are formed. The structure with acyclic fragments is obtained in the case of thiacalix[4]arenes in 1,3alternate conformation. The interaction of these compounds with a biomembrane model system was studied. It has been shown that the interaction of these compounds with model lipid membranes depends not only on the presence of hydrophilic-hydrophobic groups but also on the spatial orientation of these groups.