Die Schwingungsspektren von Trimethylsilyl-alkyl-bzw.-phenyl-aminen

Zusammenfassung Die Infrarot- und die Raman-Spektren der Silylamine (CH₃)₃Si–NH–R (R=CH₃, C₂H₅ und C₆H₅) sowie der analogen N-deuterierten Verbindungen werden mitgeteilt und analysiert. Starke Kopplungen führen zu einer Mischung vonv SiN bei etwa 700 cm^–1 mit anderen Schwingungen des C₃Si–NHR-Skelettes.

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The Infrared and Raman spectra of the silylamino compounds (CH₃)₃Si–NH–R (R=CH₃, C₂H₅, and C₆H₅) and the analogous N-deuterated species are reported and assigned. The SiN stretching mode at about 700 cm^–1 is strongly coupled with other vibrations of the molecules.

     

Demetallation of coordination compounds of nickel with tetradentate ligands based on S-substituted isothiosemicarbazides

The passage of dry gaseous hydrogen chloride through chloroform solutions or acetone suspensions of S-substituted N¹,N⁴-di(salicylidene)isothiosemicarbazidates of nickel (Ni(LRR)) has led to a demetallization reaction with the liberation in the free state of S-substituted N¹,N⁴-di(salicylidene)isothiosemicarbazides with the general formula N₂LRR (where R is H and R is CH₃ (I); R is H and R is C₂H₅ (II); R is H and R is C₃H₇ (III); R is H and R is C₇H₇ (IV); and R is CH₃ and R is CH₃ (V)). The IR spectra of (I-IV) each showed bands characteristic for an aromatic ring and groups in the 1600–1500 cm^–1 region, with a band of the deformation vibrations of an OH group at 1300 cm^–1. The PMR spectra in CDCl₃ each had two singlets at 12.15-11.25 and 9.00-8.36 ppm which were assigned, respectively, to the protons of an OH group and those of a =CH group. A multiplet in the 7.70-6.83 ppm region belonged to the protons of benzene rings. In the region of lower fields there were the signals of the substituents R and R. In the mass spectra of (I-V), the peaks of the molecular ions, and also the characteristic fragments OH, R, SR, and HSR have been detected.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 604–608, September–October, 1985.     

Structure of a new photochromic indoline spiropyran

Conclusions An x-ray diffraction structural study was carried out for the photochromic spirpyran 1,3,3-trimethyl-5-nitrospiro(indoline-2,2-[2H-1]-benzopyran). The C_spiro-O bond in the spiropyran is longer than the normal value but shorter than in the isomeric spiropyran with the nitro group in the benzopyran fragment, which is characterized by a higher quantum yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 191–194, January, 1985.     

Carbolines

4-Substituted 3, 4-dihydro--carbolines (X–XVI) were obtained by the Beckman rearrangement of oximes of -(indolyl-3)ketones (I–IV, IX) under the action of phosphorus pentachloride in nitrobenzene. 3, 4-Dihydro--carbolines were converted into -carbolines (XV–XVII) on heating with Brown's palladium catalyst in ethylene glycol. Oximes containing the aryl group react on treatment with p-toluene sulfochloride in pyridine with the formation of the arilides of -(indolyl-3)propionic acids.For preliminary report, see [18].     

Equilibrium constants of some protonated,nonprotonated and hydroxo complexes of uranium(VI) with xylenol orange

Summary The species, UO₂H₃L^–, UO₂H₂L^2–, UO₂HL^3–, UO₂L^4–, UO₂(OH)L^5– and UO₂(OH)₂L^6– are found in the equilibria between uranyl ions and 3,3-bis[N,N-di(carboxymethyl)-aminomethyl]-o-cresolsulphonphthalein (H₆L; xylenol orange; dcac) in aqueous solution. The equilibria have been studied by the potentiometric method at 25° and at an ionic strength of 0.1M (KNO₃). New algebraic equations have been employed to evaluate the equilibrium constants.     

Rhenium(V) complexes with vinyl amides

Summary The reactions oftrans-ReOCl₃(PPh₃)₂ with vinyl amides such as RCOCH=C(R)NH₂, where R = CH₂CH₂CO₂H and R = Ph and C₆H₁₃; or R = Me, CH₂CH₂CO₂Me and R = Ph, give complexes of the type ReOCl₂-[RC(O^–)=CHC(R)=NH]PPh₃, the coordination geometry of which have been deduced from i.r. and¹H n.m.r. spectroscopic data.     

Spin crossover studies in tris(N,N′-dialkyldithiocarbamato)iron(III) complexes

A series of fifteen complexes of the type [Fe(RRNCS₂)₃] with symmetric (R=R=n- C₆H₁₃, n-C₈H₁₇, CH₂–CH=;CH₂, C₆H₅, C₆H₁₁ and C₆H₅CH₂), unsymmetric (R = CH₃; R = n-C₄H₉, C₆H₁₁, C₆H₅ and R = C₂H₅; R = n-C₄H₉, C₆H₁₁, C₆H₅ and i-C₃H₇) and ring substituents (RNR=pyrrolidyl and piperidyl) have been synthesized and their magnetic moments and Mössbauer spectra recorded from room temperature (RT) to liquid nitrogen temperature (LNT). Room temperature Mössbauer spectra of all the complexes exhibit an asymmetric doublet, which could be resolved into two doublets, each corresponding to low and high spin states in equilibrium. The crystal structure of tris(N, N-diallyldithiocarbamato)iron(III) shows it to be monoclinic with trigonally distorted octahedral geometry and space group C2/c. Fe–S stretching vibrations in the far i.r. region also show equilibria, HS LS. Depending on the nature of the alkyl group substituent, variable temperature magnetic moment and Mössbauer spectral studies, all the complexes may be divided into three groups; high spin complexes exhibiting spin-crossover (⁶A_1g ²T_2g), high spin complexes exhibiting spin transition (⁶A_1g ⁴T_1g) and intermediate spin complexes showing spin transition (⁴A_1g ²T_2g). On the basis of areas of the two doublets corresponding to high and low spin states, their percent contributions were calculated. Furthermore, magnetic moments of the equilibrium mixture calculated on the basis of respective areas compare well with the experimentally determined _eff values. E_Q values for both high and low spin states show linear decrease with increasing temperature.     

Salicylaldehydo chelates of bis(cyclopentadienyl) zirconium(IV)

A new series of organometallic ionic chelates of the type [Cp ₂Zr(sal)]⁺ [ROCS₂/RRNCS₂]^–, where Hsal = salicylaldehyde;R =Me, Et, i-Pr ori-Bu andR =R =Me, Et, i-Pr;R =Me,R = benzyl orR =Et,R =m-tolyl, have been synthesized in aqueous medium by the reaction of [Cp ₂Zr(sal)]⁺Cl^– andROCS ₂ ^– K⁺/RRNCS ₂ ^– Na⁺. These compounds have been characterized by chemical analyses, electrical conductance, electronic, IR and¹H-NMR spectral studies. These studies indicate that the complexes are 1:1 electrolytes and the salicylaldehyde ligand is chelating in all these complexes. Therefore, a tetrahedral coordination about the zirconium atom is proposed.

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Salicylaldehydo-Chelate von Bis(cyclopentadienyl)-zirkonium(IV)

Zusammenfassung Eine neue Gruppe von organometallischen ionischen Chelaten vom Typ [Cp ₂Zr(sal)]⁺ [ROCS₂/RRNCS₂]^– (mit Hsal = Salicyladehyd;R =Me, Et, i-Pr oderi-Bu undR =R =Me, Et, i-Pr;R =Me,R = Benzyl oderR =Et,R =m-Tolyl) wurde in wäßrigem Medium mittels der Reaktion von [Cp ₂Zr(sal)]⁺Cl^– mitROCS ₂ ^– K⁺/RRNCS ₂ ^– Na⁺ hergestellt. Die erhaltenen Verbindungen wurden mittels chemischer Analyse, elektrischer Leitfähigkeit und der IR- sowie¹H-NMR-Spektren charakterisiert. Diese Untersuchungen zeigen, daß die Komplexe 1:1-Elektrolyte sind, wobei der Salicylaldehyd-Ligand in allen Fällen an der Chelatbildung beteiligt ist. Es wird daher für das Zirkoniumatom eine tetrahedrale Koordination vorgeschlagen.

     

Synthesis of molecular ferromagnetics [R3R′X]MCr(C2O4)3 (X = N,R = Bun,R′ = Prn,Et, Me; X = P,R = Ph,R′ = Bun; M = Mn,Fe, Co,Ni, Cu)

The synthesis, IR spectra, and the temperatures of the transition into a ferromagnetic state (T _c) of layered ferromagnetics [R₃RX[MCr(C₂O₄)₃ (M = Mn, Fe, Co, Cu, and Ni) with the [Ph₃BuP]⁺, [Bu₃RN]⁺ (R = Pr, Et, and Me) cations capable of subsequently changing the distances between metallooxalate layers have been considered. The temperatureT _c has been found to be independent of the size of the organic cation. It is believed that the determining factors in the transition to a ferromagnetic state are exchange interactions inside the metallooxalate layer.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2327–2330, September, 1996.     

Geminal systems. Communication 29. Reactions of N-chloro-N-methoxy-N′,N′-dimethylurea with N-nucleophiles

Conclusions In the reaction of N-chloro-N-methoxy-N,N-dimethylurea with amines, a nucleophilic substitution of the chlorine atom at the N atom takes place to form N-alkoxyhydrazines, which are stable in the reaction with Me₃N, pyridine, toluenesulfonamides, and give products of further transformations with Me₂NH and MeONHMe.For Communication 28 see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 606–610, March, 1986.     

Synthesis and physico-chemical studies of some polynuclear mixed carboxylate complexes of nickel(II)

A number of polynuclear mixed carboxylates of nickel(II) with the general composition [Ni(OOCCH₃)_2–n (OOCR) _n ] _x (whereR=C₁₃H₂₇, C₁₅H₃₁, C₁₇H₃₅ and C₂₁H₄₃ andn=1 or 2) have been synthesized by the transacylation reactions of anhydrous nickel acetate with higher carboxylic acids in refluxing toluene. On recrystallization from benzene-alcohol mixtures, mono-alcoholate complexes, Ni(OOCCH₃)_2–n (OOCR) _n ·ROH (whereR=CH₃ and C₂H₅) have been isolated. All these derivatives have been characterized by the molecular weight determinations, infra-red and electronic reflectance spectra and magnetic susceptibility measurements.

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Synthese und Eigenschaften einiger gemischter Carboxylat-Komplexe von Nickel(II)

Zusammenfassung Komplexe des Typs [Ni(OOCCH₃)_2–n (OOCR) _n ] _x (mitR=C₁₃H₂₇, C₁₅H₃₁, C₁₇H₃₅ und C₂₁H₄₃,n=1 oder 2) wurden aus wasserfreiem Nickelacetat mit höheren Carbonsäuren in siedendem Toluol erhalten. Bei der Kristallisation aus Benzol-Alkohol-Mischungen wurden Monoalkoholate Ni(OOCCH₃)_2–n (OOCR) _n ·ROH (mitR=CH₃ und C₂H₅) isoliert. Die Charakterisierung der Komplexe erfolgte mittels Molekulargewichtsbestimmung, Infrarot- und Elektronenspektren und der Messung der magnetischen Susceptibilität.

     

Soluble polysaccharides of Rhodotorula flava

Conclusions 1. Xanthalin has been shown to have the structure of 2, 2-dimethyl-3, 4,-diangeloyloxy-3, 4-dihydropyrano-5, 6:6, 7-coumarin on the basis of the preparation of a number of derivatives and cleavage products.2. The following products of the alkaline hydrolysis of xanthalin have been isolated and characterized for the first time: (±)-3, 4-dihydroxy-3, 4-dihydroxanthyletin (isokhellactone), C₁₄H₁₄O₅, with mp 213–215° C and (–)-trans-3-hydroxy-4-methoxy-3, 4-dihydroxanthyletin (isomethylkhellactone, C₁₅H₁₆O₅, with mp 136.5–138° C and [] _D ²⁰ –47.7 (ethanol).Khimiya Prirodnykh Soedinenii, Vol. 6, No. 1, pp. 14–19, 1970     

Synthesis and characterization of some methyl complexes of palladium(II). Part 2(1)

Summary Dichloro complexes of Pd^II, [Pd(L–L)Cl₂], where L–L=1-(thiomethyl)-2-(diphenylarsino)ethane (S–As) or 1-(thiomethyl)-2-(diphenylphosphino)ethane (S–P) andtrans-[PdL₂Cl₂], where L=diphenyl(2-phenylethyl)-phosphine (PE), diphenyl(1-naphthyl)phosphine (PN) orN-methyl-2-thiophenealdimine (SN), have been prepared and characterized. The reactions of these complexes with MeLi were investigated. The dimethyl complexes [Pd(L–L)Me₂] (L–L=S–As, S–P) and [Pd(PE)Me₂] were isolated and characterized. Reaction of [Pd(L–L)Me₂] (L–L=S–As, S–P) with HCl affords the monomethyl derivatives [Pd(L–L)Me(Cl)]. In contrast to the Pt analogues, [Pd(L–L)Me₂] and [Pd(L–L)Me(Cl)] are relatively less stable than [Pt(L–L)Me₂] and [Pt(L–L)Me(Cl)].     

The structure of xanthalin

Conclusions From the roots ofXanthogalum purpurascens growing in the Transcaucasus, we have isolated a new coumarin, C₂₄H₂₆O₇ with mp 111–113°C, [] _D ²⁰ –164.2° (c 0.97; ethanol) which we have called xanthalin. On the basis of the NMR spectrum it has been established that xanthalin is 3, 4-diangeloyl-2, 2-dimethyl-3, 4-dihydropyrano-5, 6:6, 7-coumarin.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 5, pp. 280–283, 1968     

Linear free energy relationships and the kinetics of ligand substitutions. Correlation of rate constants with overall stability constants of reactive intermediate species in the stepwise formation of tetracyanonickelate(II) from mono aminocarboxylatonickel (II) complexes

Summary A linear free energy relationship is proposed between step-wise rate constants and overall stability constants of the intermediates of the type NiL(CN)_x (where x = 0, 1 and 2) formed in the four step reaction mechanism of CN^– with NiL where L denotes aminocarboxylates viz., EDDA, NTA, HPDTA, 1,2-PDTA, TMDTA, DTPA and TTHA.EDDA: Ethylenediaminediacetic acid(N,N-1,2-ethanediylbis-glycine); NTA: Nitrilotriacetic acid[N,N-bis(carboxymethyl)glycine]; HPDTA: 2-Hydroxytrimethylenediaminetetraacetic acid(glycineN,N-(2-hydroxy-1,3-propanediyl)bis[N-(carboxymethyl)gly cine]); 1,2-PDTA: 1,2-Diaminopropanetetraacetic acid[N,N(1-methyl-1,2-ethanediyl]bis[N-(carboxymethyl)glycine]); TMDTA: Trimethylenediaminetetraacetic acid{N,N(1-methyl-1,3-ethane-diylbis[N-(carboxymethyl)glycine]}; DTPA: Diethylenetriaminepentaacetic acid (N,N-bis2[bis(carboxymethyl)amino]ethylglycine); TTHA: Triethylenetetraminehexaacetic acidN,N-ethyl-enebis{N-[2-bis(carboxymethyl)amino)ethylglycine.     

Synthesis of Boron–Nitrogen–Phosphorus Compounds from N-Silylphosphoranimines

Two modes of reactivity of N-silylphosphoranimines have been utilized to prepare the title compounds containing either B–N=P or Si–N=P–N–B linkages. First, silicon-nitrogen bond cleavage reactions of the N-silylphosphoranimines, Me₃SiN=PMe(R)OCH₂CF₃ (1: R=Me, 2: R=Ph), with various chloroboranes gave the new N-borylphosphoranimines, Ph(Me₂N)B–N=PMe₂OCH₂CF₃ (2) and [(Me₃Si)₂N](Cl)B–N=PMe₂OCH₂CF₃ (10). In other cases, however, the expected B–N=P products were unstable and cyclic phosphazenes [Me(R)P=N]_3,4 were obtained. Second, deprotonation-substitution reactions of the aminophosphoranimines, Me₃SiN=P(R)Me–N(R)H, were used to prepare a series of novel (borylamino)-phosphoranimines, Me₃SiN=P(R)(Me)–N(R)–B(NMe₂)₂ (18: R=Me, R=t-Bu; 19: R=R=Me; 20: R=Ph, R=t-Bu; 21: R=Ph, R=Me) and Me₃SiN=PMe₂–N(t-Bu)–B(Ph)X (22: X=NMe₂, 23: X=OCH₂CF₃). All of the new boron–nitrogen–phosphorus products were fully characterized by multinuclear NMR (¹H, ¹³C, and ³¹P) spectroscopy and elemental analysis.     

Rhodium(I) carbonyl complexes with α-diimine ligands containing amino or hydroxy substituents

-Diimines, RN:C(R)C(R):NR(LL) derived from glyoxal, GLL (R=H) abbreviated as GAA (R= R=4-dimethylaminophenyl) or GHA (R= R=4-hydroxyphenyl), and derived from biacetyl, BLL (R=Me) abbreviated as BDH (R=R= NH₂), BOH (R=NH₂, R=OH) react with carbonylrhodium(I) compounds to give different products depending on the imino substituents in the ligand and/or the solvent employed. The reaction of -diimines bearing amino groups, such as GAA or BDH with [RhCl(CO)₂]₂ in acetone yields binuclear [RhCl(CO)₂]₂(-LL) while in CH₂Cl₂ ionic [Rh- (CO)₂(LL)]⁺[RhCl₂(CO)₂]^– species are obtained. In acetone [RhCl(CO)₂]₂(-GAA) exists as an equilibrium mixture between two different neutral binuclear species; [Rh(CO)₂(BDH)]⁺ exists as a mixture of two species containing chelate or monodentate bonded diimine respectively. GAA or BDH react in situ with [RhCl(CO)(C₂H₄)]₂ in benzene to yield tetracoordinated monocarbonylated [RhCl(CO)(LL)] compounds. -Diimines (LL) bearing hydroxy groups, such as GHA or BOH react with [RhCl(CO)₂]₂ or [RhCl(CO)(C₂H₄)]₂ to give pentacoordinated dicarbonylated [RhCl(CO)₂(LL)] compounds.     

BISPHENYLENECOSAN as highly selective Cs+ extraction agent

A new reagent for the highly selective extraction of cesium (e-1,7–2,2)4,8–8,4-(bis--o-phenylene)bisdicarbollidocobalt(1–)ate, [(C₂B₉H₉)₂(C₆H₄)₂Co]^–, abbreviated as BISPHECOSAN is described in this paper. The choice of organic solvent and solubilizer, dependence of distribution ratio of Cs⁺ on acidity and other parameters are studied. The extraction mechanism based on selective binding of Cs⁺ cation between two phenylene rings is presented and factors influencing the chemical stability of the reagent are determined.     

Comparison of the relationships between the retention of dansyl derivatives of aliphatic amines and eluent composition for normal-and reversed-phase liquid-solid TLC systems

Summary Dansyl derivatives of four long-chain primary aliphatic amines and five secondary aliphatic amines were chromatographed in two adsorption systems: heptane+diisopropyl ether — silica and water+methanol — octadecyl cilica. In the normal-phase system R_M (log k) values were approximately linearly dependent on the log concentration of diisopropyl ether in the eluent; the separation selectivity of dansyl C₈–C₁₂ primary amines was poor. For the reversed-phase system the derivatives of both primary and secondary amines were well separated, the log k values being linearly dependent on per cent concentration of methanol in the eluent.     

Zur Reaktion von Fluorsilanen mit lithiierten Aminen

The reaction of fluorosilanes with lithium salts of bulky amines like tetramethyl-piperidine and di-tert. butylamine leads to stable aminofluorosilanes of the type R-SiF₂-NRR [R=F, C(CH₃)₃, C₆H₅, C₆H₄N(CH₃)₂]. Lithium salts of silylamines react analogously: R₂Si(NR-SiF₂R)₂ (R=R= =CH₃, R=C₆H₅). An eight membered Si–N-ring is obtained in the reaction of a disubstituted silylaminofluorosilane with the dilithium salt of a silylamine. The mass-,¹H-, and¹⁹F-NMR spectra of the above mentioned compounds are reported.