Kristallstruktur von N,N,N′,N′-Tetraisopropyl-p-phenylen-diammonium-dichlorid und-bis(tetrachloroaluminat)

Summary Protonation of the sterically overcrowded N,N,N,N-tetraisopropyl-p-phenylenediamine leads to a significant shortening of the C-N bond lengths of 7 pm as well as to a widening of the phenyl ipso-angle to 122°. All structural changes can be attributed to the twisted diisopropylammonium substituents and their electron acceptor properties.

     

N,N′-Bis(trimethylsilyl)dicyandiamide

N,N-Bis(trimethylsilyl)dicyandiamide was prepared for the first time by the reaction of dicyandiamide with hexamethyldisilazane in boiling tetrahydrofuran. Thermal transformations of this compound were studied by DTA. The novel compound may be used in the synthesis of bis(trimethylsilyl)carbodiimide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 498–500, March, 1994.     

N,N′-Bis(silylmethyl)azodicarboxamides

Russian Journal of General Chemistry - The first representatives of silicon-containing azocarboxamides, N,N′-bis(silylmethyl) azodicarboxamides, were synthesized by the reaction of...     

Five coordinate complexes of N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamide with copper Crystal and molecular structures of dichloro(N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamido)copper(II) and chloro(perchlorato)(N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamido)copper(II)

The title compound N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamide (DEAP) forms a 1:1 complex with anhydrous CuCl₂, [Cu(DEAP)Cl₂], (1) which was crystallized from EtOH solution in the monoclinic space group P2_{1/ n} with cell constant, a = 10.024(1); b = 13.122(1); c = 14.404(1) Å β = 101.31(1)° V = 1857.8(3) ų and Z = 4. The chloro-perchlorato complex, [Cu(DEAP)Cl(ClO₄)], (2) obtained in near quantitative yield by reacting (1) with an excess of NaClO₄ in EtOH, crystallized in the monoclinic space group P2_{1/ n} with cell constants, a = 7.965(1); b = 25.827(2); c = 10.046(1) Å β = 98.81(1)° V = 2042.2(4) ų and Z = 4. Both (1) and (2) contain 5-coordinated copper linked to DEAP through O～N～O donor set of atoms with covalently bonded chlorine atoms in (1) and chlorine and perchlorate groups in (2). The coordination geometry is intermediate between square pyramidal and trigonal bipyramidal, and is probably best described as a trigonally distorted rectangular pyramid.     

PVT properties of N,N,N′,N′-Tetraoctyl-3-oxapentanediamide (TODGA)

N,N,N??,N??-Tetraoctyl-3-oxapentanediamide (TODGA) is a versatile extractant for partitioning of fission products from highly active raffinate wastes. Its PVT properties are not available in literature. In this work, PVT properties of TODGA, estimated using group contribution method, are reported. A corresponding-states based equation as well as Wagner constants were also reported in the range of 273.15?K to critical temperature.     

Synthesis and Characterization of Binuclear (μ-Oxalato) Copper(II) Complexes with N,N′-Diethylethylenediamine or N,N,N′-Trimethylethylenediamine

Three new binuclear w -oxalato copper(II) complexes of composition [(Cu(N,N' -dieten) H₂O)₂ox](ClO₄)₂ ·H₂O (1) (N,N'-dieten = N,N'-diethylethylenediamine, H₂ox = oxalic acid), [(Cu(trimeen)H₂O)₂ox](ClO₄)₂·2H₂O (2) (trimeen = N,N,N'-trimethylethylenediamine) and [(Cu(trimeen)H₂O)₂ox](NO₃)₂ ·2H₂O (3) have been isolated from the reactions of Cu(ClO₄)₂ ·6H₂O (or Cu(NO₃)₂ ·3H₂O), the appropriate amine and Na₂ox in water and have been characterized by IR and electronic spectroscopy and magnetic measurements. The crystal structure of [(Cu(N,N' -dieten)H₂O)₂ ox](ClO₄)₂.H₂O (1) has been determined by single-crystal X-ray analysis. The structure of ( 1 ) consists of binuclear cations [(N,N'-dieten)H₂O)Cu(ox)Cu(N,N'-dieten)H₂O)]²⁺, perchlorate anions and water molecules of crystallization. The copper atom is coordinated by two oxygen atoms of the oxalato ligand, two nitrogen atoms belonging to N,N'-dieten and one oxygen atom of water in a distorted square-pyramidal arrangement. The temperature dependence of magnetic susceptibilities (78-293 K) was measured for 1-3 . Magnetochemical measurements show that copper(II) ions in these compounds are antiferromagnetically coupled with J = -172 cm^-1, -172 cm^-1 and -168 cm^-1 (H = -2JS ₁ S ₂, S ₁= S ₂ = 1/2) for 1, 2 and 3, respectively.     

Extraction of U(VI) and Th(IV) from nitric acid solutions with N,N,N′,N′-tetrahexylsuccinylamide

The results of monitoring of⁸⁵Kr volume activity in ground-level air of Prague over the period 1989–1995 are summariyed. Seasonal dependence with a maximum in late spring and summer months and a gradual increase of⁸⁵Kr concentration in the atmosphere were observed. Linear approximation of long-term trend in the period 1983–1995 gives the growth rate of 35 mBq·m^–3 per year. Exponential approximation provides an inter-year growth by 3.7% The measured values were compared to the prognosis of⁸⁵Kr contamination development of the atmosphere from the early 1980s. They were found to be near to the low estimate of the assumed development.     

Catalase activity of cobalt(II) complexes with N,N,N′,N′-tetrasubstituted thiocarbamoylsulfenamides

On the base of the kinetic and activation parameters of the hydrogen peroxide decomposition in the presence of chelates of CoX₂ salts (X = Cl, Br, I, NCS) with N,N,N′,N′-tetrasubstituted thiocarbamoylsulfenamides containing exocyclic (out-of-chelate) fragments of dimethylamine (I), piperidine (II), and piperazine (III) the nature of acido-ligands influence on catalase activity of complexes I–III was revealed, depending on the structure and composition of the chelating ligand. Mononuclear complexes I(Br) and II(Br) can transform into 10-membered binuclear macrochelate intermediates.     

cis-Bis[N1,N2-bis(trimethylsilyl)benz­amidinato-κ2N1,N2]chloro(4-tolyl­imido-κN)vanadium(V)

The title complex, [V(C₇H₇N)(C₁₃H₂₃N₂Si₂)₂Cl], consists of a V metal centre coordinated to five N atoms and a Cl⁻ ion in a pseudo-octahedral arrangement. The N atoms of the benzamidinate ligands form two four-membered chelate rings to V, with bite angles of 63.59 (8) and 64.36 (8)°, whilst the fifth N atom is from a p-tolyl­imido ligand [V—N—C 172.2 (2)°] located cis with respect to the Cl⁻ ion [Cl—V—N_imido 96.96 (8)°].     

Poly(N,N′-dichloro-N-ethyl-benzene-1,3-disulfonamide, N,N,N′,N′-tetrachlorobenzene-1,3-disulfonamide, poly(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide, and N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide catalyzed formylation of amines and alcohols using ethyl formate under microwave irradiation

A simple, rapid, and efficient procedure for formylation of primary and secondary amines and alcohols using ethyl formate catalyzed with poly(N,N′-dichloro-N-ethyl-benzene-1,3-disulfonamide (PCBS), N,N,N′,N′-tetrachlorobenzene-1,3-disulfonamide (TCBDA), poly(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide (PBBS) and also N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide (TBBDA) was adopted. The reactions were performed under microwave irradiation with high yields.     

Manganese(II), nickel(II) and copper(II) complexes of (1,3-bis-aminomethyl) cyclohexane-N,N,N′,N′-tetrakisbenzimidazole

Summary Mn^II, Ni^II and Cu^II complexes of (1,3-bis-aminomethyl)-cyclohexane-N,N,N,N-tetrakisbenzimidazole (CDTB) have been prepared and characterized by spectral techniques. The complexes are monomeric and pseudo-octa-hedral, as evidenced by their e.p.r. spectra and analytical data. Parameters ², ², ² and for Cu^II complexes, and the crystal field splitting parameter (10 Dq) together with the Nephelauxetic ratio (), for Ni^II complexes, are reported.     

[N,N′-(4-Methyl-4-azaheptane-1,7-diyl-κN)bis(4-methoxysalicylideniminato-κ4O,N,N′,O′)]cobalt(II) ethanol hemisolvate

The title compound, [Co(C₂₃H₂₉N₃O₄)]·0.5C₂H₆O or [Co^II{(4-MeO-sal)₂Medpt}]·0.5CH₃CH₂OH [(4-MeO-sal)₂Medpt is N,N′-(4-methyl-4-aza­heptane-1,7-diyl)­bis(4-methoxysalicyl­iden­iminate)], obtained through the reaction of H₂[(4-MeO-sal)₂Medpt] and Co(CH₃COO)₂ in refluxing ethanol under an atmosphere of ultrapure nitro­gen, has the usual pseudo-trigonal-bipyramidal coordination arrangement previously found for this class of (sal)₂Rdpt compounds. The O—Co—O bond angle [120.4 (1)°] is significantly smaller than the corresponding values previously found for most non-O₂-bound [Co^II{(sal)₂Medpt}]-type mol­ecules (observed range 126.9–138.6°), whereas the equatorial Co—N bond [2.185 (3) Å] is relatively long.     

Radiolysis of cerium(III) 1,2-bis(β-aminoethoxy)ethane N,N,N′,N′-sodium sulfonate triacetic acid chelate

The publication describes chelation studies of cerium(III) with 1,2-bis(-aminoethoxy)-ethane N,N,N,N-sodium sulfonate triacetic acid (ASTA). The results showed the effectiveness of ASTA as a chelating agent by molar ratio, continuous variation and slope ratio methods. Stable 11 complex was formed at pH from 4 to 8. Aqueous solutions of the chelate of different mole ratios at pH and 7.5 were irradiated by -radiation with different doses. The results show that a decrease of absorbance with increasing absorbed dose was obtained in the dose range studied. A proposed radiolytic mechanism is discussed. The degradation of ligand was due to OH radical.     

Synthesis and X-ray crystal structures of N,N,N′,N′-tetraalkylpyridine-2,6-dithiocarboxamides (S-dapt) complexes of cobalt(II) and nickel(II)

Reactions of anhydrous CoX₂ (X?=?Br^?, SCN^?) and Ni(ClO₄)₂ with N,N,N′,N′-tetraisobutylpyridine-2,6-dithiocarboxamides (S-dbpt), N,N,N′,N′-tetraisopropyl pyridine-2,6-dithiocarboxamides (S-dppt), and N,N,N′,N′-tetraethylpyridine-2,6-dithiocarboxamides (S-dept) lead to the formation of [Co(S-dbpt)Br₂] (1), [Co(S-dppt)(SCN)₂] (2), and [Ni(S-dept)₂]·(ClO₄)₂·H₂O (3), respectively. The X-ray crystal structures of the three S-dapt ligands and three complexes along with spectroscopic analyzes are presented. The molecular structure investigations of the S-dapt ligands show that the thiamide planes are twisted with respect to the pyridine ring, which is more in the case of phenyl groups. The structures of the Co(II) complexes reveal that an increase in steric crowding on the amide side arms of the ligands has no substantial effect on the geometry adopted by the corresponding complexes. The Co(II) gives only 1?:?1 five-coordinate, ion-paired complexes with a distorted square pyramidal geometry. Ni(II), on the other hand, prefers an octahedral geometry with 1?:?2 metal–ligand ratio. The coordination behavior of S-dapt has been compared to the analogous oxo(O-daap) ligands. Lesser propensity of S atom to get involved in H-bonding interactions ensures an S-N-S type of tridentate coordination by S-dapt.     

Ring Closure of N,N′:N,N′-bis(decamethylene)-1, 4-diamino-2,5-bis(10-cyanodecyloxy)benzene (IV)

Recently, β-chloro-α,β-unsaturated carbonyl compounds have become increasingly useful as intermediates in organic synthesis. For example, reactions involving a number of different cyclic β-chloro-α,β-unsaturated ketones with a variety of reagents (a malonate anion², the anion of the dithiolane derivative of ethyl glyoxalate³, zinc-silver couple in methanol⁴, dimethylsulfoxonium methylide^5,6) have produced a series of structurally diverse and potentially fruitful synthetic intermediates. The second-mentioned reagent has also been successfully reacted with a β-chloro-α,β-unsaturated ester³.     

Cobalt(II) and copper(II) complexes ofN,N′,N″,N‴-tetra(2-cyanoethyl)-1,4,8,11-tetraazacyclotetradecane

Summary Cobalt(II) and copper(II) complexes of the title ligand, TCEC, as well as a cobalt(II) complex ofN,N,N",N'-tetra (1-methyl-2-cyanoethyl)-1,4,8,11-tetraazacyclotetradecane, TMCEC, have been isolated and spectrally characterized.     

Syntheses of 6N(N′-formyl-D-phenylalanyl)-deoxyamino-β-cyclodextrin and 6N(N′-formyl-L-phenylalanyl)deoxyamino-β-cyclodextrin and their inclusion behavior

6N(N-formyl-D-phenylalanyl)-deoxyamino--cyclodextrin and 6N(N-formyl-L-phenylal-anyl)-deoxyamino--cyclodextrin (I andII) were prepared. These new hosts formed intramolecular host-guest complexes and included naphthyl derivatives preferentially with a stoichiometry of 1:1. The inclusion behavior was different between I and II because the cavity shape formed with the CD cavity and the phenylalanine moiety of I was different from that of II.     

N,N,N′,N′-四丁基丙二酰胺萃取Tb(Ⅲ)的研究

取代酰胺类萃取剂因其易合成、分解产物易除去而不影响萃取工艺流程等优点 ,在核燃料后处理方面显示出很好的应用前景。国内外在该类萃取剂萃取铀 (Ⅵ )、钍 (Ⅳ )以及硝酸的性能研究方面已经做了大量工作[1 ,2 ] ,但对高放废液中共存稀土元素的萃取研究报道较少[3] 。本文报道Ｎ ,Ｎ ,Ｎ′ ,Ｎ′ 四丁基丙二酰胺 (ＴＢＭＡ)在不同稀释剂中萃取Ｔｂ(Ⅲ )的性能。1　实验1 1　试剂和仪器试剂均为ＡＲ级。ＴＢＭＡ实验室合成 ,减压蒸馏提纯 ,经元素分析、红外光谱等检验产品为目标产物 ,纯度高于 98%。ＦＴＳ 1 65红外光谱仪 (美国Ｂｉｏ Ｒ…     

N,N,N′,N′-四丁基丙二酰胺萃取Yb(Ⅲ)的研究

取代酰胺类萃取剂易合成、分解产物易除去可用于萃取铀 (Ⅳ )、钍 (Ⅳ ) [1 - 4 ] ,但对高放废液中共存稀土元素的萃取研究较少[5] 。本文在以前研究工作的基础上[6] ,进一步探讨了TBMA萃取Yb(Ⅲ )的性能。1　实验部分1 1　试剂和仪器试剂均为AR级。TBMA由实验室合成 ,减压蒸馏提纯 ,经元素分析、红外光谱等检验产品为目标产物 ,纯度高于 98%。FTS 1 65红外光谱仪 (美国Bio Rad公司 ) ,75 2分光光度计 (上海分析仪器总厂 ) ,PHS 2C精密数显酸度计 (上海伟业仪器厂 ) ,恒温康氏振荡器 (实验室改装 )。1 2　实验准确称量 1 970 3g…     

N,N,N＇,N＇-四丁基丙二酰胺萃取Tb(Ⅲ)的研究

取代酰胺类萃取剂因其易合成、分解产物易除去而不影响萃取工艺流程等优点,在核燃料后处理方面显示出很好的应用前景.国内外在该类萃取剂萃取铀(Ⅵ)、钍(Ⅳ)以及硝酸的性能研究方面已经做了大量工作[1,2],但对高放废液中共存稀土元素的萃取研究报道较少[3].