Flavonoids ofHaplophyllum perforatum. New glycosides of limocitrin

Two new glycosides of limocitrin have been isolated from the epigeal part ofHaplophyllum perforatum (M. B.) Kar. et Kir. On the basis of chemical transformations and spectral characteristics the structures of the substances isolated have been established as 7-(6-acetyl--D-glucopyranosyloxy)-3,4,5-trihydroxy-3,8-dimethoxyflavone and 7-[0--L-rhamnopyranosyl-(1 2)--D-glucopyranosyloxy]-3,4,5-trihydroxy-3,8-dimethoxyflavone.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 192–196, March–April, 1985.     

Zur Mannich-Reaktion von Dihydro-6-methyl-2(1H)-pyrimidinonen

Zusammenfassung Dihydro-4,4,6-trimethyl-2(1H)-pyrimidinone reagieren mit Formaldehyd und sekundären bzw. primären Aminen zu 6-Dialkylaminoäthylidentetrahydro-2(1H)-pyrimidinonen bzw. Hexahydro-2(1H)-pyrido[4,3-d]Pyrimidinonen. Mit Succindialdehyd bzw. Glutardialdehyd und primären Aminen entstehen 5,7-Äthanohexahydro-2(1H)-pyrido[4,3-d]pyrimidinone bzw. Tetrahydro-6,8-propano-6H-pyrimido[1,6-c]pyrimidin-1(2H)-one. Die 6-Dialkylaminoäthylidentetrahydro-2(1H)-pyrimidinone geben mit Phenolen Tetrahydrospiro([1]benzopyran-2,4(1H)-pyrimidin)-2(3H)-one, mit cycl. -Dicarbonylverbindungen Hexahydrospiro([1]benzopyran-2,4(1H)-pyrimidin)-2,5(3H, 6H)-dione bzw. Tetrahydrospiro(2H,5H-pyrano[3,2-c][1]benzopyran-2,4(1H)-pyrimidin)-2(3H),5-dione bzw. mit Malonestern -(Tetrahydro-4,4-dimethyl-2-oxo-6-pyrimidyl)-äthylmalonester.Zusammenfassung Dihydro-4.4.6-trimethyl-2(1H)-pyrimidinones react with formaldehyde and sec. and prim. amines resp. to 6-dialkylaminoethylidentetrahydro-2(1H)-pyrimidinones and hexahydro-2(1H)-pyrido[4.3-d]pyrimidinones, resp. succindialdehyde and glutaraldehyde with primary amines give 5.7-ethanohexahydro-2(1H)-pyrido[4.3-d]pyrimidinones and tetrahydro6.8-propano-6H-pyrimido[1.6-c]pyrimidin-1(2H)-ones, resp. 6-Dialkylaminoethylidentetrahydro-2(1H)-pyrimidinones react with phenols to tetrahydrospiro([1]benzopyran-2.4(1H)-pyrimidin)-2(3H)-ones, with cyclic -dicarbonyl compounds to hexahydrospiro([1]benzopyran-2.4 (1H)-pyrimidin)-2,5 (3H), 6H)-diones and tetrahydrospiro(2H,5H-pyrano[3.2-c][1]benzopyran-2.4(1H)-pyrimidin)-2(3H),5-diones, resp., with malonates -(tetrahydro-4.4-dimethyl-2-oxopyrimidyl-6)-ethylmalonates.

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Mannich reaction with dihydro-6-methyl-2(1H)-pyrimidinones

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Herrn Prof. Dr.F. Kuffner zum 65. Geburtstag gewidmet.     

Photooxidation of bis(ethylxanthato)nickel(II) containing aromatic nitrogen heterocyclic ligands in chloroform

The photochemistry of the complexes [Ni(Etxn)₂(N-N)] [Etxn=ethylxanthate,N-N=2,2-bipyridine(bpy), 4,4-dimethyl-2,2-bipyridine (4,4-Me-bpy), 1,10-phenanthroline (phen) or 2,2-bipyrimidine (bpym)] has been investigated. These complexes were not light sensitive in most solvents such as acetonitrile. Upon irradiation of chloroform solutions of these complexes, a photoredox reaction occurred giving the parent Ni(Etxan)₂. It is suggested that the reactive excited state is of the charge-transfer-to-solvent (CTTS) type. The energy of this state depends on the redox potentials of the solvent. When CHCl₃ as solvent was replaced by the stronger oxidant CCl₄, the photoactive wavelength region was shifted to the red. It was blue shifted when the weaker oxidant CH₂Cl₂ was used. From quantum yield measurements it is concluded that the photostability of the studied complexes decreases in the following order:bpym>phen>bpy>4,4-Me-bpy.

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Photooxidation von Bis(ethylxanthato)nickel(II) mit aromatischen Stickstoffheterocyclen enthaltenden Liganden in Chloroform

Zusammenfassung Es wurde die Photochemie der Komplexe [Ni(Etxn)₂(N-N) [Etxn=Ethylxanthat,N-N=2,2-Bipyridin (bpy), 4,4-Dimethyl-2,2-bipyridin (4,4-Me-bpy), 1,10-Phenanthrolin (phen) oder 2,2-bipyrimidin (bpym)] untersucht. Diese Komplexe waren in den meisten Lösungsmitteln wie etwa Acetonitril nicht lichtsensitiv. Bei Bestrahlung von Chloroformlösungen der Komplexe trat jedoch eine Photoreaktion auf, die zum Stammkomplex Ni(Etxn)₂ führte. Es wird vorgeschlagen, für den reaktiven angeregten Zustand einen Charge-Transfer-zu-Lösungsmittel (CTTS)-Typ anzunehmen. Die Energie dieses Zustands hängt vom Redoxpotential des Lösungsmittels ab. Bei Ersatz von CHCl₃ als Lösungsmittel durch das stärkere Oxidans CCl₄ wurde die photoaktive Wellenlänge nach Rot verschoben. Eine Blauverschiebung ergab sich hingegen, wenn das schwächere Oxidans CH₂Cl₂ verwendet wurde. Aus Messungen der Quantenausbeuten ergab sich die folgende Ordnung nach abnehmender Photostabilität der untersuchten Komplexe:bpym>phen>bpy>4,4-Me-bpy.

     

Mono and dinuclear cationic rhodium(I) and iridium(I) complexes with sulphur donor and group Vb ligands

Summary Rhodium(I) and iridium(I) mixed complexes of the formulae [M(diolefin)LL]ClO₄, [M(diolefin)L₂L]ClO₄, [(diolefin)LIr(-L)₂IrL(diolefin)](ClO₄)₂, [(diolefin)LM(-L-L)ML'(diolefin)](ClO₄)₂, [(diolefin)Rh{-(L-L)}₂Rh(PPh₃)₂](ClO₄)₂ and [(diolefin)LIr{-(L-L)}₂IrL (diolefin)](C1O₄)₂, (L=monodentate sulphur ligand, L-L=bidentate sulphur ligand, L=group Vb ligand; M=Rh, diolefin=1,5-cyclooctadiene (COD) or 2,5-norbornadiene (NBD); M=Ir, diolefin=COD) are described.Author to whom all correspondence should be directed.     

Cobalt(II) and nickel(II) chloride and bromide complexes of 2-(2′-methyl-8′-quinolyl)benzoxazole and 2-(2′ or 4′-methyl 8′-quinolyl)benzimidazole

Summary Cobalt(II) and nickel(II) halide complexes of the ligands 2-(2-methyl-8-quinolyl)benzoxazole (mqbo), 2-(2-methyl8quinolyl)benzimidazole (mqbi) and 2-(4-methyl-8-quinolyl)benzimidazole (mqbi) were synthesized and characterized by analytical, thermogravimetric, conductivity and magnetic data, and i.r. and electronic spectra.The ligands are bidentate N-donors yielding complexes where the coordination geometry depends on the metal ion and steric hindrance. All the cobalt complexes have formula [CoL₂X₂] and distorted tetrahedral geometry. Different types of nickel compounds were obtained: i) complexes of formula NiLX₂ · n H₂O (or EtOH) (L = mqbo or mqbi; n=0–1.5) which arepseudo-tetrahedral or five-coordinate and ii) complexes NiL₂X₂ · n H₂O (L = mqbi, n=3 or 4) where the metal is bound to four nitrogen atoms and the overall coordination geometry is tetragonal. The structural changes occurring after removal of water or alcohol from the complexes are also reported.     

Half-sandwich metal diselenolate complexes Cp#M(NO)(SePh)2 (M = Mo or W; Cp# = Cp or MeCp) as ligands. Synthesis of selenolate-bridged heterobimetallic compounds

The reactions of half-sandwich diselenolate Mo and W complexes Cp^#M(NO)(SePh)₂ (M = Mo; Cp^# = Cp (1a), MeCp (1b); M = W; Cp^# = Cp (1c)) with (Norb)Mo(CO)₄, Ni(COD)₂ and Fe(CO)₅ have been investigated. Treatment of (1a), (1b) and (1c) with (Norb)Mo(CO)₄ in PhMe gave the bimetallic complexes: CpMo(NO)(-SePh)₂Mo(CO)₄ (2a), MeCpMo(NO)(-SePh)₂Mo(CO)₄ (2b) and CpW(NO)(-SePh)₂Mo(CO)₄ (2c) in moderate yields. Irradiation of (1a) and (1c) in the presence of Fe(CO)₅ gave heterobimetallic complexes CpMo(CO)(-SePh)₂Fe(CO)₃ (3a) and CpW(NO)(-SePh)₂Fe(CO)₃ (3c). Ni(COD)₂ reacts with two equivalents of (1a), (1b) and (1c) to give [CpMo(NO)(-SePh)₂]₂Ni (4a), [MeCpMo(NO)(-SePh)₂]₂Ni (4b) and [CpW(NO)(-SePh)₂]₂Ni (4c) in good yields. The new heterobimetallic complexes were characterized by i.r., ¹H-n.m.r., ¹³C-n.m.r. and EI-MS spectroscopy.     

Chromium(III) and oxovanadium (IV) complexes of some urea derivatives

Summary The preparation of eight new complexes of Cr^III and VO^IV with urea derivatives is reported here. The ligands used were 2-imidazolidinone (ethyleneurea, EU),N,N'-dimethyl-2-imidazolidinone (N,N -dimethylethyleneurea, DMEU), 2-imidazolidinethione (ethylenethiourea, ETU), andN, N, N, N -tetramethyl-2-imidazolidone (tetramethylurea, TMU). The previously reported complex VOCl₂(TMU)₂ was also prepared. All nine complexes were investigated with regard to conductimetry as well as visible and i.r. spectroscopy. All carbonyl-containing complexes exhibit a metal-oxygen bond, whereas in ETU complexes a metal-nitrogen bond seems to be favoured.     

Spectrophotometric determination of vanadium with 4-(1′H-1′,2′,4′-Triazolyl-3′-azo)-2-methylresorcinol

Summary 4-(1H-1,2,4-Triazolyl-3-azo)-2-methylresorcinol reacts with vanadium(V) at pH 8.10 (Tris-HClO₄ buffer solution) to produce a pink-violet 11 complex ( _max=525 nm,=2.55×10⁴l·mol^–1· cm^–1) in a 50% (v/v) methanol-water medium, which allows the spectrophotometric determination of 0.1 to 1.51 ppm of vanadium. The method has been applied for the determination of the vanadium content in low alloy steels.

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Spectrophotometriscbe Bestimmung von Vanadin mit 4-(1H-1,2,4-triazo-lyl-3-azo)-2-methylresorcin

Zusammenfassung Vanadin bildet bei pH 8,10 (Tris-HClO₄-buffer) mit 4-(1H-1,2,4-tri-azolyl-3-azo)-2-methylresorcin ein rosenrot-violettes Chelat, dessen Absorptionsmaximum bei 525 nm in Gegenwart von 50% Methylalkohol gemessen wird. Dieser 11-Komplex entspricht bei einer Vanadin-Konzentration von 0,1–1,51g/ml dem Beerschen Gesetz; seine molare Absorptivität ist 2,55×10⁴l·mol^–1·cm^–1. Das Verfahren wurde zur Bestimmung des Vanadins in Stahl verwendet.

     

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.     

Synthesis of novel heterocycles from thiazolecarbohydrazides

Cyclization of 2-methyl (or -phenyl)-5-phenylthiazole-4-carbohydrazides (1) and (2) under various conditions gives differing oxadiazoles: 2-(2-substituted-5-phenyl-4-thiazolyl)-1,3,4-oxadiazole-5-thiones (7) and (8), and 2-(2-substituted-5-phenyl-4-thiazolyl)-1,3,4-oxadiazoles (9) and (10). Cyclodehydration of thiazolecarbonyl-thiosemicarbazides (3)–(6) with NaOH givesthe 3-(2-substituted-5-phenyl-4-thiazolyl)-4-substituted-4H-5-mercapto-1,2,4-triazoles (11)–(14), while H ₃ PO ₄ gives the 2-(2-substituted-5-phenyl-4-thiazolyl)-5-phenylamino-1,3,4-thiadiazoles (15) and (16).A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 679–683, March, 1992.     

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)].     

Synthesis of obtusinin and 7-(3′-hydroxymethylbut-2′-enyloxy)-6-methoxy-2H-1-benzopyran-2-one

Obtusinin (1) has been synthesised by the reaction of 6-methoxy-7-(3-methylbut-2-enyloxy)-2H-1-benzopyran-2-one (3) with OsO₄. Synthesis of 7-(3-hydroxymethylbut-2-enyloxy)-6-methoxy-2H-1-benzopyran-2-one (2) has been achieved by the regiospecific oxidation of3 with SeO₂ followed by reduction of the formed aldehyde with KBH₄.

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Synthese von Obtusinin und 7-(3-Hydroxymethylbut-2-enyloxy)-6-methoxy-2H-1-benzopyran-2-on

Zusammenfassung Obtusinin (1) wurde über 6-Methoxy-7-(3-methylbut-2-enyloxy)-2H-1-benzopyran-2-on (3) mit OsO₄ synthetisiert. Die Darstellung von 7-(3-Hydroxymethylbut-2-enyloxy)-6-methoxy-2H-1-benzopyran-2-on (2) wurde mittels regioselektiver Oxidation von3 mit SeO₂, gefolgt von Reduktion des gebildeten Aldehyds mit KBH₄, bewerkstelligt.

     

Entropy in dissimilarity and chirality measures

Within the prospect of quantifying the geometrical dissimilarity of molecular models on the basis of a thermodynamical formalism, the algebra of stereogenic pairing equilibria is reviewed and applied to molecular geometry: developing Rassat's proposition, an interaction energy of two figures F and F is taken as proportional tod _H ^Emphasis>/2 (F, F), whered _H denotes the Hausdorff distance. IfG is a group of rotations in E _n the geometrical version of the general equation (E) of the chemical algebra defines a distance extensionD _p(F,F) ofd _H(F,F), which is independent of the orientations of F and F, and where the coefficientp is interpreted as the reciprocal of a temperature-like parameter:p 1/T. At K (p = ), no formal entropy contributes to the definition of the uniform distanceD . At K (p = 0), the discrimination between homo- and hetero-pairing of figures by the harmonic distance Do is averaged over orientation states. Temperature-dependent chirality measuresc _p are derived fromD _p, andc is analogous to Mislow's chirality measure. If T and oT are normalized enantiomorphic triangles with coincident centroids inE ₂,c _p(T) =D _p (T, T) is calculated forp = 0 andp = , and discussed for 0 <p < . Finally, the Hausdorff interaction model is putatively related to energy profiles versus dihedral angle inmeso- anddl-molecules.     

Kinetics and mechanism of nucleophilic substitution of dichloro{1-methyl-2-(arylazo)imidazole}palladium(II) by pyridine bases

The reaction of dichloro{1-methyl-2-(arylazo)imidazole}palladium(II), Pd(RaaiMe)Cl₂ where RaaiMe = p-R–C₆H₄N=N–C₃H₂N₂-1-Me; R = H(1), Me(2), Cl(3), with pyridine bases [RPY: R = H (a), 4-Me (b), 4-Cl (c), 2-Me (d), 2,6-Me₂ (e), 2,4,6-Me₃ (f)] has been studied spectrophotometrically in MeCN at 451 nm. The products (4) have been isolated and characterised as trans-Pd(RPy)₂Cl₂. The kinetics of the nucleophilic substitution has been examined under pseudo-first-order conditions at 298 K. A single phase reaction step has been observed for bases such as Hpy (a), 4-MePy (b) and 4-ClPy (c) and follows the rate law: rate = (a + k[RPy]²[Pd(RaaiMe)Cl₂]). The bases 2-MePy (d), 2,6-Me₂Py (e) and 2,4,6-Me₃Py (f) exhibits a bi-phasic reaction and follows the rate laws: rate–1 = (a + k[RPy][Pd(RaaiMe)Cl₂]) and rate–2 = (a + k[RPy][Pd(RaaiMe)-Cl₂]), where k is the third-order rate constant; k is the second-order first phase rate constant, k is the second-order second phase rate constant and a/a/a correspond to the solvent dependent constant of the respective reaction path. The rate data supports a nucleophilic association path. External addition of Cl^– (LiCl) suppresses the rate, which follows the order: k/k/k (3) > k/k,k (1) > k/k,k (2). The k values are linearly related to the Hammett constants. The 2-substituted pyridines (d–f) remarkably reduce the rate and show a bi-phasic reaction behaviour as compared with 4-Rpy (a–c). This is attributed to the steric effect that destabilises the transition state. The rate decreases with increasing steric crowding at the ortho-position and follows the order: (d) > (f) > (e). The 4-substituted pyridines control the rate via an inductive effect and follow the order: (b) > (a) > (c).     

Salen and tetrahydrosalen nickel(II) and copper(II) complexes

The synthesis and characterisation of novel bis salen complexes, M(salenH2), N,N-bis-[5(1,1,3,3-tetramethyl- butyl)salicylidene]-1,2-diaminoethane complexes, (M=Ni or Cu), and the corresponding less studied, bis-tetrahydrosalen complexes, M[H2(salenH2)], N,N-bis-[2-hydroxy-5(1,1,3,3-tetramethylbutyl)benzyl]-1,2-diaminoethane complexes, (M=Ni or Cu), with a highly branched substitution pattern at C-5 of the benzene ring is described. The Schiff bases behave as dibasic tetradentate ligands. The tetrahydrosalen complexes show structural properties, chemical and thermal behaviour which is different from those of the corresponding salen complexes. The melting points and decomposition temperatures of these complexes were determined by d.s.c. and t.g.a.     

The solid-state structure of (+)-(i)-menthyl 2-formamido-4, 4,4-trifluorobutanoate and the hydrogenation of the 2-butenoate precursor

Hydrogenation ofZ-(–)-(1R, 3R, 4S)-menthyl 2-formamido-4,4,4-trifluoro-2-butenoate catalyzed by Pd/C was performed at atmospheric pressure to yield a mixture of (2R, 1R, 3R, 4S)- and (2S, 1R, 3R, 4S)-menthyl 2-formamido-4,4,4-trifluorobutanoate diastereomers in a 5545 ratio, respectively. Repeated fractional crystallization from ethyl acetate and vapor diffusion of petroleum ether afforded (+)–(2S, 1R, 3R, 4S)-menthyl 2-formamido-4,4,4-trifluorobutanoate as clear colorless, crystalline prisms which were subjected to single-crystal X-ray diffraction analysis. The crystals belong to the orthorhombic system P2₁2₁2₁, and at 213 K:a=5.054(1),b= 10.000(2),c=32.707(1) Å,V=1652.9(4) ų,Z=4,R(F)=0.040, andR _w (F)=0.037. The finding of the (2S)-configuration for the formamido-acid portion of the (+)-ester enabled the configurational assignment of the asymmetric hydrogenation products ofZ-methyl 2-formamido-4, 4,4-trifluoro-2-butenoate catalyzed by chiral diphosphine/rhodium(I) complexes.     

Synthesis and Characterization of Solid Coordination Complexes of Diamides for Uranium(VI) and Thorium(IV)

Five kinds of solid coordination complexes of uranium(VI) and thorium(IV) with the diamide (N,N,N,N-tetrabutylmalon-amide (TBMA), N,N,N,N-tetrabutylsuccinylamide (TBSA), N,N,N,N-tetrabutylglutaramide (TBGA), N,N,N,N-tetrabutyl-adipicamide (TBAA)) were synthesized. All these complexes of UO₂(NO₃)₂·TBMA, UO₂(NO₃)₂· TBSA, [UO₂(NO₃)₂·(TBGA^1/2)₂] _x , UO₂(NO₃)₂·TBAA and Th(NO₃)₄·2TBMA were characterized by elemental analysis, UV spectra, IR spectra and ¹³C NMR spectra. The coordination form and proposed structures of the complexes are also discussed.     

Phthalocyaninartige Bor-Komplexe

Zusammenfassung Aus Halogenboranen und Organohalogenboranen (RBX ₂R=C₆H₅, Cl, Br;X=F, Cl, Br) sowie aus Organoboranen oder Thioboranen entstehen mit Phthalodinitril Triisoindolo-[1,2,3-cd1,2,3-gh1,2,3-kl][2,3a,5,6a,8,9a,9b]-hexaazaboraphenalene von denen die B–Cl- und B–F-Verbindungen näher charakterisiert werden.Dekaboran(14), Diboran(6) oder Boranaddukte von Stickstoffbasen liefern hingegen mit Phthalodinitril metallfreies Phthalocyanin.

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Triisoindolo[1,2,3-cd1,2,3-gh1,2,3-kl][2,3a,5,6a,8,9a,9b]-hexa-azaboraphenalene

Triisoindolo[1,2,3-cd1,2,3-gh1,2,3-kl][2,3a,5,6a,8, 9a,9b]-hexaazaboraphenalenes are obtained from the reactions of haloboranes and organohaloboranes (RBX ₂R=C₆H₅, Cl, Br;X=F, Cl, Br) as well as from organoboranes or thioboranes with phthalodinitrile. The B–Cl and B–F compound have been characterized by analyses, i.r.-, u.v.- and mass-spectrometry.Diborane(6), dekaborane(14) and amine-boranes, however, upon reaction with phthalodinitrile lead to high yields of metal free phthalocyanine.

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Herrn Prof. Dr.M. Pailer zum 60. Geburtstag gewidmet.     

Diacetylenic Derivatives of Fe2(CO)6(μ-EE′): Spectroscopic Investigations of Fe2(CO)6{μ-EC(H) = C(C≡ CMe)E′} (E = E′, E ≠ E′; E, E′ = S, Se, Te)

The diacetylenic adducts, Fe₂(CO)₆{-EC(H) = C(C CMe)E} (E = E, E E; E, E = S, Se, Te) (1–8) have been obtained from the room temperature stirring of Fe₂(CO)₆(-EE) with HC CC CMe in methanol solvent containing sodium acetate. Compounds 1–8 have been characterized by IR and multinuclear NMR (¹H, ¹³C, ⁷⁷Se, and ^l25Te) spectroscopy. Trends in the chemical shifts of ⁷⁷Se and ¹²⁵Te NMR spectra of Fe₂(CO)₆{-EC(H) = C(C CMe)E} with a variation of EE are discussed.     

Thermal and some other properties of the complexes crystallizing from the system Ni(II)-en-[Ni(CN)4]2−-H2O

Seven complex compounds exhibiting the compositions Ni(en)₃Ni(CN)₄·H₂O (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄·2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2.5H₂O (VI) and-Ni(en)₂Ni(CN)₄ (VII) were prepared from the system Ni-en-[Ni(CN)₄]^2–-H₂O. These compounds were examined by the methods of infrared spectroscopy, X-ray powder diffractometry, UV-VIS reflectance spectroscopy, and also by the measurement of magnetic moments. The thermal stability, the stoichiometry of thermal decomposition and the mutual transformations were investigated with a derivatograph. The reactions proceeding according to the following schemes were observed if the system was heated to appropriate temperature: (I)(II)(III)(V)(IV) and (VI)(VII)(III)(V)(IV) Process (VII)(III) represents isomerization. The reversibility of the process (V)(IV) is due to the high hygroscopicity of the anhydrous complex. The changes in structure in the course of the individual processes are discussed.

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Zusammenfassung Aus einem System Ni-en-[Ni(CN)₄]^2–-H₂O wurden sieben Komplexe der Formeln Ni(en)₃Ni(CN)₄·H₂O (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄·2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2.5H₂O (VI) und-Ni(en)₂Ni(CN)₄ (VII) hergestellt. Diese Verbindungen wurden mittels IR-Spektroskopie, Röntgenpulverdiffraktometrie, UV-Reflexionsspektroskopie und durch Messungen des magnetischen Momentes untersucht. Die Wärmestabilität, die Stöchiometrie des thermischen Zerfalles und die gegenseitigen Umwandlungen wurden mittels eines Derivatographen untersucht. Wird das System auf geeignete Temperaturen erhitzt, kann der Reaktionsverlauf durch folgendes Schema dargestellt werden: (I)(II)(III)(V)(IV) und (VI)(VII)(III)(V)(IV).Der Prozeß (VII)(III) verkörpert eine Isomerisierung. Die Umkehrbarkeit von Prozeß (V)(IV) ist auf die ausgeprägten Hygroskopieeigenschaften des wasserfreien Komplexes zurückzuführen. Es werden die im Ablaufe der einzelnen Prozesse vorgehenden Strukturveränderungen besprochen.

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Ni- -[No(N)]² -₂ Ni(en)₃Ni(CN)₄ · ₂ (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄-2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2,5H₂O (VI) -Ni(en)₂Ni(CN)₄ (VII). , , - , . , . (I)(II)(III)(V)(IV) (VI)(VII)(III)(V)(IV). (VII)(III) . (V)(IV) . .