Showing papers by "Vladimir P. Fedin published in 2013"
TL;DR: In this article, the catalytic performance of the metal-organic framework Cr-MIL-101 in solvent-free coupling of CO2 and epoxides to produce cyclic carbonates has been explored at both high-pressure (100 ǫ CO2) and low pressure (8 ǔ CO2), in the temperature range of 25-120 c.
248 citations
TL;DR: In this paper, the properties of Fe-MIL-101 and Cr-ML-101 metal-organic frameworks in the solvent-free oxidation of cyclohexene and α-pinene with molecular oxygen have been explored.
188 citations
TL;DR: In this article, the catalytic properties of the metal-organic framework Cr-MIL-101 in solvent-free cycloaddition of CO2 to epoxides to produce cyclic carbonates using tetrabutylammonium bromide as co-catalyst have been explored under mild reaction conditions (8 bar CO2, 25 0C).
66 citations
TL;DR: The reaction of [Mo6I14](2-) with methyl propiolate HC≡CC(O)OMe in the presence of Ag(+) and Et3N yielded the new luminescent complex, the first fully organometallic complex in the family of octahedral {M6X8} clusters.
Abstract: The reaction of [Mo6I14]2– with methyl propiolate HC≡CC(O)OMe in the presence of Ag+ and Et3N yielded the new luminescent complex [Mo6I8(C≡CC(O)OMe)6]2–, the first fully organometallic complex in the family of octahedral {M6X8} clusters. The cluster was crystallized as tetraphenylphosphonium salt and characterized by X-ray single-crystal diffraction and elemental analyses, mass spectrometry, 13C NMR, UV–vis, and luminescence spectroscopies.
56 citations
TL;DR: The molecular recognition and self-assembly between host cucurbit[6]uril and guest adrenaline led to kinetic trapping and crystallization of the intermediate exclusion complex, which was characterized by X-ray diffraction.
27 citations
TL;DR: New Ru-containing polyoxometalate was obtained in high yield by reaction of [Ru(NO)Cl5](2-) with [PW11O39](7-) and characterized by multinuclear NMR, cyclic voltammetry, IR spectroscopy, and electrospray ionization mass spectrometry (ESI-MS).
Abstract: New Ru-containing polyoxometalate [PW11O39RuII(NO)]4- (14-) was obtained in high yield by reaction of [Ru(NO)Cl5]2- with [PW11O39]7- and characterized by multinuclear NMR, cyclic voltammetry, IR spectroscopy, and electrospray ionization mass spectrometry (ESI-MS). The intrinsic reactivity of the {RuNO} site in 14- toward various reagents has been studied using a versatile and simple ESI tandem mass spectrometric methodology for identification of the L attached at the Ru site; this approach relies on the preferential liberation of the L ligands attached at the Ru sites upon mass-selecting desired intermediates and subsequent promotion of their fragmentation. Reactions with both hydrazine and hydroxylamine lead to elimination of the nitroso group and quantitative formation of [PW11O39RuIII(H2O)]4- (24-) in aqueous solution. In the reaction with hydroxylamine, an intermediate with coordinated dinitrogen has been detected. An easy access to the NH3-coordinated [PW11O39RuNH3]4- (34-) complex was achieved upon ...
27 citations
TL;DR: The complex [Na4((CH3)2CO)15][PtBi2I12]·3(CH32CO (1) has been prepared by the reaction of BiI3, NaI and H2[PtCl6]·6H2O and structurally characterized using X-ray diffractometry and represents the first example of a polyiodobismuthate with an octahedral heterometallic unit.
Abstract: The complex [Na4((CH3)2CO)15][PtBi2I12]·3(CH3)2CO (1) has been prepared by the reaction of BiI3, NaI and H2[PtCl6]·6H2O and structurally characterized using X-ray diffractometry. It represents the first example of a polyiodobismuthate with an octahedral heterometallic unit. Interatomic interactions in the [PtBi2I12]2− anion were characterized using the topological methods QTAIM and ELF.
26 citations
TL;DR: In this article, three new homochiral metal-organic frameworks (MOFs) based on malate anions and N-donor linkers of different lengths have been prepared.
23 citations
TL;DR: A new thiolate cluster complex was synthesized by the metathesis reaction of (Bu4N)2[Mo6I14] and HC6F4SAg in methylene chloride.
Abstract: A new thiolate cluster complex (Bu4N)2[Mo6I8(SC6F4H)6] was synthesized by the metathesis reaction of (Bu4N)2[Mo6I14] and HC6F4SAg in methylene chloride. According to the X-ray structure determination, the cluster core {Mo6I8}4+ coordinates six thiolate ligands 2,3,5,6-HC6F4S−. The Mo-Mo and Mo-I distances have their usual values. The average Mo-S distance is 2.538(4) A, and the Mo-S-C angles range from 107 to 109°. Compound (Bu4N)2[Mo6I8(SC6F4H)6] both in solid and in solution displays a bright red microsecond luminescence, which is typical of octahedral molybdenum halide complexes.
23 citations
01 Jan 2013
TL;DR: In this paper, the main emphasis is on synthesis, structure, stability, reactivity, and cluster core rearrangements, while spectroscopic and other information is given more selectively.
Abstract: This chapter is devoted to the inorganic cluster compounds of transition elements. The term ‘cluster’ denotes a compound containing three or more metal atoms held together at least in part by metal–metal bonds. As this chapter needs to fall within the scope of inorganic chemistry, the coverage of organometallic examples and complexes with organic ligands is restricted. What is left is the vast world of cluster halides, chalcogenides, mixed chalcohalides, and oxides in low oxidation states. Almost all transition element clusters have been routinely characterized by x-ray structural analysis. The main emphasis is on synthesis, structure, stability, reactivity, and cluster core rearrangements, while spectroscopic and other information is given more selectively.
22 citations
TL;DR: In this article, two novel Zn-and Cd-containing coordination polymers, [Zn 6 (H 2 O) 3 (DMf) 6 (ur) 2 (tdc) 6 ]·4 H 2 O ( 1 ) and [Cd 6 (Cd 2 O), 3 (dmf)6 (ur), 2 (TDc) 2(tdc), were synthesized and characterized by the methods of single crystal X-ray diffraction, IR, TG and elemental analysis.
TL;DR: In this paper, the catalytic performances of Cr-MIL-101 and Fe-Mil-101 porous coordination polymers were investigated in the allylic oxidation of alkenes, including natural terpenes, with molecular oxygen (1 atm) under mild solvent-free conditions.
Abstract: The catalytic performances of Cr-MIL-101 and Fe-MIL-101 porous coordination polymers have been investigated in the allylic oxidation of alkenes, including natural terpenes, with molecular oxygen (1 atm) under mild solvent-free conditions. Both catalysts remain stable under optimal conditions (40°C for Fe-MIL-101 and 60°C for Cr-MIL-101) and can be recycled, at least, four times without loss of the catalytic properties. Fe-MIL-101 favours the formation of unsaturated alcohols, while Cr-MIL-101 mediates the formation of unsaturated ketones. The oxidation process involves the formation of alkene hydroperoxide via conventional radical chain process and its further transformations over the MIL-101 catalysts. The mechanism of the hydroperoxide transformation strongly depends on the metal nature.
TL;DR: In this article, the first case reaction yields the layered coordination polymerLi 3 [(Rh 2 (CH 3 COO) 4 ) 2 (PW 12 O 40 )] 12.5 H 2 O(1), where polyoxoanions are coordinated via oxygen atoms tothe {Rh 2 } 4+ core.
TL;DR: A unique step-by-step activation of the biporous material via formation of the intermediate host-guest complex with a labile ligand has been presented on the example of the metal-organic framework.
Abstract: A unique step-by-step activation of the biporous material via formation of the intermediate host–guest complex with a labile ligand has been presented on the example of the metal–organic framework [Zn4(ur)2(ndc)4]. The difference in the chemical environment of channels allows highly selective separation of the mixture of S4N4 and benzene.
TL;DR: In this article, cuboidal cuboidal metal-chalcogenide framework bearing chiral α-hydroxy and amino acids has been used for triangulation of triangular clusters.
TL;DR: In this article, the three host-guest complexes between the cucurbit[6]uril macrocycle and the catecholamine drug isoprenaline obtained in the presence of magnesium or calcium ions were investigated.
Abstract: We report on the three host–guest complexes between the cucurbit[6]uril macrocycle and the catecholamine drug isoprenaline obtained in the presence of magnesium or calcium ions. The metal ions affect both the crystallization pathway of the CB6–isoprenaline complexes and the supramolecular architecture in the solid state. In the case of the magnesium cations the sequential crystallization of the metal-free and the magnesium containing forms of the host–guest complexes was observed, while the use of calcium cations resulted in the direct crystallization of the calcium-coordinated CB6–isoprenaline complex.
TL;DR: Mesoporous chromium(iii) terephthalate MIL-101 was treated with aqueous solutions of sodium fluoride, chloride, and bromide and the properties of the resulting compounds to sorb nitrogen, hydrogen, and methane were studied.
Abstract: Mesoporous chromium(iii) terephthalate MIL-101 was treated with aqueous solutions of sodium fluoride, chloride, and bromide. The properties of the resulting compounds to sorb nitrogen, hydrogen, and methane were studied. The methane sorption was shown to depend on the nature of the inserted halide ion. The treatment with a sodium chloride solution leads to an increase in the methane uptake by MIL-101.
TL;DR: In this paper, a layered coordination polymer [Zn2(Nmp)2(Tdc)2] · 2Nmp · 0.5H2O, which was characterized by IR spectroscopy, elemental and thermogravimetric analyses, and luminescence measurements.
Abstract: Heating of zinc(II) nitrate and 2,5-thiophenedicarboxylic acid (H2Tdc) in the presence of hexamethylenetetramine in N-methylpyrrolidone (Nmp) gave the crystals of a layered coordination polymer [Zn2(Nmp)2(Tdc)2] · 2Nmp · 0.5H2O, which were studied by X-ray diffraction. The compound was characterized by IR spectroscopy, elemental and thermogravimetric analyses, and luminescence measurements.
TL;DR: In this article, a static method with glass membrane-gauge manometers in the systems host (metal-organic framework [Zn 4 (dmf)(ur) 2 (ndc) 4 ]) and guests (benzene, water) within the temperature range 316-K to 470-K was used.
TL;DR: The ability to tune the capsule's skeletal softness is demonstrated by adding linker-type units to a solution/dynamic library containing tungstates and providing options to influence differently important capsule-substrate interactions.
Abstract: Addition of [Mo2VO2(μ-O)(μ-S)(aq)]2+ linker-type units to a solution/dynamic library containing tungstates results via the formation of the complementary pentagonal {(W)W5} units logically in the self-assembly of a mixed oxide/sulphide {WVI72MoV60}-type Keplerate, thereby demonstrating the ability to tune the capsule's skeletal softness (the (μ-O)2 and (μ-S)2 scenarios are known) and providing options to influence differently important capsule–substrate interactions.
TL;DR: In this paper, the isotherms of benzene sorption by the metal-organic coordination polymer [Zn2(bdc)2(dabco)] were studied within the temperature range 25-90°C at pressures up to 75-torr.
Abstract: The isotherms of benzene sorption by the metal–organic coordination polymer [Zn2(bdc)2(dabco)] were studied within the temperature range 25–90 °C at pressures up to 75 torr. The maximal benzene content in [Zn2(bdc)2(dabco)] at room temperature was demonstrated to correspond to the composition [Zn2(bdc)2(dabco)]·3.8C6H6. It was established that the process of benzene desorption from the substance under investigation occurs in three stages. (1) Evaporation of benzene from the phase of variable composition (phase C) with compression and distortion of the unit cell (the composition of the phase C varies from [Zn2(bdc)2(dabco)]·3.8C6H6 to [Zn2(bdc)2(dabco)]·3.2C6H6). (2) The transformation of the phase C into phase P. The phase P has the same unit cell geometry as that for the empty framework. The maximal benzene content is [Zn2(bdc)2(dabco)]·1.0C6H6. (3) Benzene evaporation from the phase P of variable composition. We studied the temperature dependences of the equilibrium vapor pressure of benzene for the samples with compositions [Zn2(bdc)2(dabco)]·3.0(3)C6H6 and [Zn2(bdc)2(dabco)]·2.0(3)C6H6 within the temperature range 290–370 K. The thermodynamic parameters of benzene vaporization were determined for the latter compound (
$$ \Updelta {\text{H}}_{{{\text{av}} .}}^{o} = 49\left( 1 \right) \,{\text{kJ }}\left( {{\text{moleC}}_{6} {\text{H}}_{6} } \right)^{ - 1} $$
; $$ \Updelta {\text{S}}_{{{\text{av}} .}}^{^\circ } = 100\left( 3 \right)\, {\text{J}}\left( {{\text{moleC}}_{6} {\text{H}}_{6} {\text{K}}} \right)^{ - 1} $$
; $$ \Updelta {\text{G}}_{298}^{^\circ } = 19.0\left( 2 \right)\, {\text{kJ}}\left( {{\text{moleC}}_{6} {\text{H}}_{6} } \right)^{ - 1} $$
).
TL;DR: In this article, the crystal structure of 1 was determined by a single crystal X-ray diffraction analysis (space group R{ie638-1}c, a = 12.0042(2) A, c = 52.6879(11) A and V = 6575.2
Abstract: [Pt3S2(P(CH2OH)3)6](PF6)(OH)·H2O (1) is obtained by a reaction of [Pt3S2(P(CH2OH)3)6]Cl2 with NH4PF6. The crystal structure of 1 was determined by a single crystal X-ray diffraction analysis (space group R{ie638-1}c, a = 12.0042(2) A, c = 52.6879(11) A, V = 6575.2(2), Z = 6, C18H57F6O20P7Pt3S2, d
x = 2.385 g/cm3, T = 150 K, R
1 = 0.044 for 2123 F
0 > 4δ(F) until 2θmax = 63°). The cations contain a {Pt3(μ3-S)2}2+ core with nonbonding Pt…Pt distances of 3.1536(6) A. The Pt atoms are in a square planar environment; the Pt-S and Pt-P bond lengths are 2.3586(16) A and 2.260(2) A respectively.
TL;DR: In this paper, the reaction of NiCl2 · 6H2O and P(CH2OH)3 (THP) with H2S and (H7O3)2[Mo6Cl14] · 3H 2O in ethanol produces new trinuclear nickel sulphide complex [Ni3(μ3-S)2{(HOCH2)2PCH2OP(CH 2OH)2}3]
Abstract: Reaction of NiCl2 · 6H2O and P(CH2OH)3 (THP) with H2S and (H7O3)2[Mo6Cl14] · 3H2O in ethanol produces new trinuclear nickel sulphide complex [Ni3(μ3-S)2{(HOCH2)2PCH2OP(CH2OH)2}3][Mo6Cl14] · 0.8H2O (I) with new bidentate phosphine-phosphinite ligand resulted from THP condensation. It was characterized by X-ray structure analysis.
TL;DR: Three polyoxotungstates of SnII, PdII, and RhII, Na8[H2SnW12O42]·nH2O [1, n = 22.75 (1a) and n = 31.10 (1b)], Na2K(H)[Pd(H2Os)4][H2W 12O48{Pd
Abstract: Three polyoxotungstates of SnII, PdII, and RhII, Na8[H2SnW12O42]·nH2O [1, n = 22.75 (1a) and n = 31.10 (1b)], Na2K(H)[Pd(H2O)4][H2W12O48{Pd(H2O)3}2]·10H2O (2), and Na8[Rh2(H2O)2(W5O18)2]·21.25H2O (3) were obtained. The complexes were characterized by X-ray analysis, solid-state 1H NMR spectroscopy, IR spectroscopy, thermogravimetric analysis, and elemental analysis.
TL;DR: In this paper, a solution of cadmium nitrate and isonicotinic acid in N,N′-dimethylformamide or dimethyl sulfoxide gave three new coordination polymers.
Abstract: Heating a solution of cadmium nitrate and isonicotinic acid in N,N′-dimethylformamide or dimethyl sulfoxide gave three new coordination polymers, [Cd(Inic)2] · 0.5DMF (I), [Cd3(DMSO)6(Inic)2(SO4)2] (II), and [{Cd(DMSO)(Inic)}2(SO4)] · 2H2O (III), which were studied by X-ray crystallography. Compounds I and III were characterized by IR spectroscopy and elemental and thermogravimetric analyses and luminescence spectroscopy.
TL;DR: The crystal structures of triclinic and monoclinic modifications of Nb thiobromide NbS2Br2 were determined by X-ray analysis.
Abstract: The crystal structures of triclinic and monoclinic modifications of Nb thiobromide NbS2Br2 are determined by X-ray analysis Both modifications possess layered structures in which {Nb2(μ-S2)2}4+ cluster units are connected by bridging bromides into 2D layers ∞2[Nb2(S2)2Br8/2] The two polymorphs differ only in the way in which the layers are stacked Interatomic distances and bond angles are identical for both polymorphs
TL;DR: The crystal structure of the [Ta6Br12(H2O)6]-BPh4)2·4H 2O salt was determined by X-ray crystallographic analysis.
Abstract: The crystal structure of the [Ta6Br12(H2O)6](BPh4)2·4H2O salt (1), obtained from Ta6Br14·7H2O and NaBPh4, is determined by X-ray crystallographic analysis. The structure contains a network of hydrogen bonds, which organizes the cluster cations into layers.
TL;DR: Chiral metal-organic coordination polymers were synthesized from aqueous or water-methanol solutions of potassium hydrogen saccharate and a salt of the corresponding metal.
Abstract: Chiral metal-organic coordination polymers [Co2(sacch)2]·1/2H2O·CH3OH (1), [Cu(sacch)(H2O)2]·3H2O (2), and [Mg(H2O)3(sacch)] (3) (H2sacch is d-saccharic acid) were synthesized from aqueous or water-methanol solutions of potassium hydrogen saccharate and a salt of the corresponding metal. The compositions and structures of the resulting compounds were determined by single-crystal X-ray diffraction and confirmed by X-ray powder diffraction, IR spectroscopy, thermogravimetry, and elemental analysis.
TL;DR: In this paper, the reaction of VO(OPr)3] (Pr is n-propyl) with hexamethyldisylthiane Me3SiSSiMe3 in the presence of β-diketones (acetylacetone, Hfac, and dipivaloylmethane (Dpm)), is studied.
Abstract: The reaction of [VO(OPr)3] (Pr is n-propyl) with hexamethyldisylthiane Me3SiSSiMe3 in the presence of β-diketones (acetylacetone (HAcac), hexafluoroacetylacetone (Hfac), and dipivaloylmethane (Dpm)), is studied. In all cases, vanadium(IV) and vanadium(III) β-diketonate complexes of different types are formed. New crystalline modification [V(Acac)3] is obtained in the reaction with HAcac. The mixedligand vanadium(III) complex of the composition [V2(Hfac)2(μ-OPr)]2 is formed with Hfac. In the presence of Dpm, the known vanadium(IV) complex [V2O2(Dpm)2(μ-OPr)2] is obtained in which two vanadyl groups VO2+ are linked by two bridging propoxy groups. The structures of all products are determined by X-ray diffraction analysis.
TL;DR: In this article, the authors investigated the electrical conductivity of aniline polymerized inside nanopores of chromium terephthalate dielectric matrix MIL-101 and found that the main contribution to a net conductivity is caused by contacts between particles of the polyaniline.
Abstract: We investigated an electrical conductivity of aniline polymerized inside nanopores of chromium terephthalate dielectric matrix MIL-101. We found that temperature dependences of conductivity (T) are described by the fluctuation-induced tunneling model, which means that the main contribution to a net conductivity is caused by contacts between particles of the polyaniline. We also found that the nanoporous matrix affects the composite conductivity via the size reduction of the conducting polyaniline phase encapsulated in the pores. Dependence of conductivity from a current was thoroughly investigated. This dependence is resulted from a reduction of energy gap for current carriers which is, in turn, induced by an increasing electric field applied.