Synthesis,structure, and properties of trinuclear pivalate {Zn2Eu} complexes with N-donor ligands

New luminescent heterometallic complexes of Eu³⁺ and Zn²⁺ were synthesized: Zn₂Eu(NO₃)(Piv)₆(L)₂ (Piv is pivalate anion, L = MeCN (1), 2,3-lutidine (2), 2,2′-bpy (3)) and [Zn₂(Piv)₃(2,2′-bpy)₂][ZnEu(NO₃)₃(Piv)₃(2,2′-bpy)] (4). In the case of 2,2′-bpy, the order of mixing of the reagents ([Zn(Piv)₂] _n , Eu(NO₃)₃·6H₂O, and 2,2′-bpy) affects the composition of the final reaction product: the reaction of [Zn(Piv)₂] _n and Eu(NO₃)₃·6H₂O (in the ratio Zn : Eu = 3 : 1) in MeCN affords complex 1 and the subsequent addition of 2,2′-bpy (Zn : L = 1 : 1) affords complex 3. Complex 4 is formed in the reaction of [Zn(Piv)₂] _n and 2,2′-bpy (Zn : L = 1 : 1) in MeCN followed by the addition of Eu(NO₃)₃·6H₂O (Zn : Eu = 3 : 1). The luminescence spectra of compounds 1–4 (Zn : Eu = 3 : 1) exhibit metal-centered luminescence of Eu³⁺. The most efficient ligand-antenna is 2,2′-bpy, which is due to the optimum position of the triplet level of this ligand.     

Heteroligand complexes of Nd(III), Yb(III), and Er(III) dibenzoyl methanates with bis(5-pyridin-2-yl-1,2,4-triazol-3-yl)methane

Heteroligand coordination compounds Ln(Dbm)₂HL · nEtOH, where Ln is Nd(III), Yb(III), and Er(III); HDbm is dibenzoylmethane; H₂L is bis(5-pyridin-2-yl-1,2,4-triazol-3-yl)methane, are synthesized and studied. The complexes are studied by elemental analysis, TGA, and IR spectroscopy. The structure of complex [Nd(Dbm)₂ · HL · EtOH] · EtOH is determined by X-ray diffraction analysis. The crystals are triclinic, space group $P\bar 1$ , a = 10.2004(9), b = 11.3809(10), c = 20.9173(18) Å, α = 102.133(1)°, β = 103.568(1)°, γ = 100.306(2)°; Z = 2 (8416 reflections with I > 2σ(I), R = 0.053, Rw = 0.136). The luminescence of solid samples of the studied complexes is studied in the near-IR region.     

Synthesis and fluorination of nitro-substituted thionocarbonates

Thiocarbonylchloride reacts with -nitroalcohols yielding symmetrical thionocarbonates. Transesterification of bis(2-fluoro-2,2-dinitroethyl)thioncarbonate affords alkyl 2-fluoro-2,2-dinitroethylthionocarbonates. Fluorination of these thionocarbonates yields the corresponding difluoroformals.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 375–376, February, 1993.     

Electrochemical synthesis of π-indenyl-π-(3)-1,2-dicarbollyliron(III)

Co-electrolysis of potassium 1,2-dicarbadodecahydroundecaborate and indene in 0.1N sodium bromide solution in dimethylsulfoxide using iron electrodes afforded -indenyl--(3)-1,2-dicarbollyliron(III).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 764–765, April, 1993.     

Metallation of the methyl group ino-nitrosotoluene: synthesis and the molecular structure of the binuclear complex [o-(NO)(CH2)C6H4)]2Pd2(μ-OOCCF3)2

The reaction of the tetranuclear cluster Pd₄(CO)₄(OOCCF₃)₄ witho-nitrosotoluene afforded the Pd¹¹-containing complex [o-(NO)(CH₂)C₆H₄]₂Pd₂(μ-OOCCF₃)₂. The elimination of CO₂ and the formation of organic products of transformation of tolylnitrene species (azotoluene, ditolylamine, and tolylisocyanate) were observed in the course of the reaction. The title complex was characterized by IR and¹H NMR spectroscopy. Its structure was established by X-ray diffraction analysis. It was suggested that the reaction proceeds through intermediate formation of nitrene complexes. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 147–150, January, 2000.     

Synthesis and structure of o-bis(2-fluoro-2,2-dinitroethyl)-nitromethyl ester of 2′-fluoro-2′, 2′-dinitroethyl-2″-fluoro-2″-nitroethylenecarboxime

Conclusions The product of conversion of O-bis(2-fluoro-2,2-dinitroethyl)nitromethylbis(2-fluoro-2,2-dinitroethyl)carboxime in methanol or ether is O-bis(2-fluoro-2,2-dinitroethyl)nitromethyl-2-fluoro-2,2-dinitroethyl-2'-fluoro-2-nitroethylenecarboxinie, the structure of which has been established by x-ray diffraction analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2019–2021, September, 1987.     

Vicinal N,C-difluorination of secondary polynitroalkylamine Mannich bases

The direct fluorination of Mannich bases containing nitro groups in one or two alkyl substituants in the position relative to the amine nitrogen gives previously unreported vicinal N,C-difluorides.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1692–1693, July, 1991.     

Kinetics of carbon dioxide absorption from air in a flow reactor with a fixed bed of K<Subscript>2</Subscript>CO<Subscript>3</Subscript>-based sorbent

Sorption of carbon dioxide from air in a flow reactor with a bulky fixed bed of the K₂CO₃/Al₂O₃ composite sorbent was studied. The dynamic sorption capacity of the material was shown to depend on the relative humidity of the inlet air. A numerical model was constructed for evaluating the profile of СО₂ concentration in the layer and kinetic curves of CO₂ breakthrough at the outlet of the reactor. The results of simulation allowed us to adequately describe the experimental kinetic curves at 20–40% humidity.     

Peculiarities of the nitration of secondary polynitroalkanes

Conclusions In the interaction of salts of 1,1,1,3,5,5,5-heptanitro- or 1,5-difluoro-1,1,3,5,5-pentanitropentanes with nitrating systems based on HNO₃, 1,1,1,3,3,5,5,5-octanitro- or 1,5-difluoro-1,1,3,3,5,5-hexanitropentanes, 1,1,1,5,5,5-hexanitro- or 1,5-difluoro-1,1,5,5-tetranitropentan-3-ones, the O-bis-(2,2,2-trinitroethyl)nitromethyl ether of bis(2,2,2-trinitroethyl)carboxime or the O-bis(2-fluoro-2,2-dinitroethyl)nitromethyl ether of bis(2-fluoro-2,2-dinitroethyl)carboxime are formed. The ratio of the reaction products depends on the composition of the nitrating system. The data obtained permit us to consider that the nitrating reagent is a nonionized form of HONO₂ or AcONO₂.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1357–1361, June 1986.