Volume 33, Issue 10

The double decomposition of (TDBA)LiPc(2-) with halocomplexes of the lb-elements is investigated in nonpolar aprotic solvents. Phthalocyanines of the formula MLiPc(2-) are isolated only for the univalent cations Cu(I) and Ag(I), but not for Au(I). The impure AgLiPc(2-) is light sensitive. In contrast to earlier observations only oxidation products of the phthalocyanine anion are obtained in the presence of Cu(II) and Au(III). The preparation of Ag(II) and Au(II) phthalocyanines failed.

Lithiumphthalocyanine(1-), to date the most simple representative of radical phthalocyanine species, is prepared in nonpolar aprotic solvents by the chemical, electrochemical and photochemical oxidation of quarternary ammonium phthalocyanines(2-). The compound is characterized by its electronic and vibrational spectra.

(CF 3 SO 2 NSO 2 ) 2 (1), a compound with a four-membered ring, was prepared from CF 3 SO 2 NSO and SO 3 . 1 as well as (FSO 2 NSO 2 ) 2 form 1:1 adducts with S 4 N 4 , pyridine and pyridine carbonitrile-4 (2a-2f). By comparison with FSO 2 NCOS 4 N 4 it was shown that a dipolar type of addition had occured. In contrast the reaction of 1 and (FSO 2 NSO 2 ) 2 with aromatic nitriles yields 1:2 cycloaddition products (3a-3g) which were characterized on the basis of mass spectra. The six-membered rings of 4a-4b which contain carbon, nitrogen and sulfur atoms were obtained from the reaction of isocyanates with (FSO 2 NSO 2 ) 2 or (CF 3 SO 2 NSO 2 ) 2 . 4-BrC 6 H 4 NCO and SO 3 react in a similar way to yield 5. The starting materials are extremely sensitive to moisture while most of the adducts can be handled in open air without decomposition.

In the course of our investigation of the ternary system K-Au-Sn we obtained the new compound KAu 4 Sn 2 . Its crystal structure has been determinated from single crystal X-ray diffraction data. It crystallizes in the tetragonal space group 1̅4̅c2 with unit-cell parameters a = 884.7 and c = 817.8 pm and Z = 4. The structure is comparable to that of the Tl 2 Se.

The compounds NaMgAs and NaMgSb were prepared and their structures determined by powder and single crystal data. NaMgAs and NaMgSb crystallize in a modified Cu 2 Sb-type-structure, space group P 4 /nmm-D 7 4h . The cell parameters for the tetragonal com-pounds are:

The syntheses and the IR and 1 H NMR spectra of the new cations [ƞ 5 -C 5 H 5 Ru(CO) 2 L] + (L=CH 3 CN, propene, cyclohexene, PPh 3 , PEt 3 , NH 3 ,CNCH 3 ) , {[ƞ 5 -C 5 H 5 Ru(CO) 2 ] 2 PP} 2+ and [ƞ 5 -C 5 H 5 Ru(CO)PP] + (PP=Ph 2 PCH 2 CH 2 PPh 2 ) are described.

Nonstoichiometric iron (III) oxichloride is capable of intercalating a large number of guest molecules with Lewis base character, e.g. dimethylsulfoxide, formamide, hexa-methylphosphortriamide, or alkylamines, while the reactions of stoichiometric FeOCl are restricted to pyridine and its derivatives only. The nonstoichiometric host lattice can be synthesized either by direct reaction form Fe 2 O 3 , FeCl 3 and Fe or by reduction of the stoichiometric compound. In the latter case the basal spacings of the intercalation complexes depend upon the degree of reduction and the electrolyte concentration. The highly expanded lattice is rapidly hydrolyzed in the presence of water.

The symmetric N-organomercury-triazenes C 6 H 4 X-N = N-N(HgC 6 H 5 )-C 6 H 4 X (X = H, 2-F, 2-Cl, 2-Me, 2-NO 2 , 3-Cl, 3-NO 2 , 4-Cl, 4-Me and 4-NO 2 ) were prepared. IR and PMR measurements indicate monodentate structures associated with rapid C 6 H 5 Hg exchange in solution. MS and UV data are given.

The visible and near-ultraviolet spectrum of rhodium(II)acetate hydrate single crystals has been measured in a temperature range from 10 K to 295 K. Two band systems centered at 17,000 cm -1 and 22,000 cm -1 have been found, both consisting of components polarized parallel to and perpendicular to the rhodium-rhodium z-axis. Polarizations, intensities and temperature dependences are consistent with an assignment of z-polarized a 1g →a 2u and xy-polarized e g →a 2u transitions for the lower energy band. For the higher energy band it could not be determined definitely whether only the b 2g →-b 1u and e g → b 1u transitions give rise to the z-and x,y-polarization directions, respectively, or if b 1g → b 2u and e g →b 2u also make a contribution.

Cobalt(II)-M-hexacyanoferrate(II), M = K, NH 4 , Cs, as synthetic sorbents have ion exchange properties selective for monovalent cations. They show a higher selectivity for the ions with larger crystal radius if the sorption takes place in dilute solutions, whereas in concentrated sulutions the selectivity sequence is reversed. The phenomenon is attributed to the differences in physico-chemical properties of the given pair of competing ions in the solution phase and to steric limitations in the phase of ion exchanger.

The adduct of 2,2,2-trifluoro-4,4,5,5-tetrakis(trifluoromethyl)-1,3,2 A 5 -dioxaphospholane with trimethylphosphine crystallises in the orthorhombic space group Pbcm, Z = 4, with a - 11.018(2), b - 12.978(4), c= 11.607(2) Å at -120 °C. The perfluoropinacolyl ring system lies in a crystallographic plane of symmetry. This ring conformation and the very long endocyclic C-C bond and average C-CF 3 distances of respectively 1.59(1) and 1.59(1) A are presumably a consequence of very short F···F steric contacts. The P→P bond distance of 2.234(5) is very short for a coordinate bond being only 0.01-0.03 A longer than that typically observed for a a-bond. The tr-bond lengths to the hexacoordinate phosphorus are influenced by the nature of the Zrans-bond in the octahedron.

The dehydration decomposition of cadmium and manganese hydrogen orthoarsenate monohydrates was studied by static isothermal and differential thermoanalytical methods. It was found that the dehydration decomposition takes place in a single stage forming the respective diarsenate, the peak minimum temperature being 458 K for the cadmium and 466 K for the manganese salt.

A new vanadium-cobaltcarbonyl-cluster, cyclopentadienyl-vanadylidyne-tricobaltennea-carbonyl, has been prepared and identified by IR and masspectrometric measurements.

The crystal structure of the diamagnetic title compound (1), a = 9.9594(9), b = 9.3895(7), c = 14.8434(8), β = 95.112(5) is described. Two co-ordinatively square planar nickel atoms each carrying a h 3 -C 5 H 9 group are linked together by two methyl bridges, with the h 3 -C 5 H 9 groups lying cisoid about the two nickel atoms. The molecule is folded about its centre so that the Ni-Ni distance is only 2.371, indicating a strong interaction within the unsaturated metal system. The bridging methyl groups form novel, slightly unsymmetrical two electron - three centre bonding systems. The electronic structure of 1 is analysed by MO methods. The nature of the nickel-nickel interaction as well as the stabilising factors of these unsaturated systems are explained. A discussion centred about one low energy LUMO leads

The influence of the exchangeable monovalent cations on the vibrations of the frame-work of Y zeolite has been studied. A regular shift of the frequencies of some absorption bands is observed and described as a function of interaction between the exchangeable cation and the oxygen from the zeolite framework. The linear dependence of the fre-quencies of some absorption bands and the reciprocal of the sum of ionic radii of the cation and the framework oxygen suggests that the exchanged cations: Na + , Ag + , K + and Tl + are occupying similar positions in the zeolite lattice. Li + and Cs + ions do not obey this regularity. The present IR studies agree with the results of chemical analysis of the studied zeolites.

A series of new coordination compounds is reported with 1,2,5-oxadiazole (ODZ) as the ligand, viz. [M(ODZ) 3 ](SbCl 6 ) 2 with M = Mg(II), Mn(U), Fe(II), Co(II), Ni(II), and Zn(II). The metal ions are in a regular octahedral environment of six nitrogen atoms. The ligands function as bidentate bridges between the metal ions.

Transition Metal-Tyrosine Complexes, Oxidation Tyrosine and the copper(II), cobalt(II) and nickel(II) complexes of this amino acid have been oxidized with potassium nitrosodisulfonate. The chemical oxidation follows the enzymatic pathway, i.e. the Raper-Mason mechanism through the intermediate of dopachrome. The complexes take a considerable shorter reaction time compared with uncomplexed tyrosine. Analytical and spectroscopic data of the resulting black oxidation products indicate a composition comparable with that of natural melanines.

Ethyl diazoacetate (2 a) and tert-butyl diazoacetate (2 b) are converted into the metal stabilized, doubly bridging alkoxycarbonyl carbenes upon photolysis with (ƞ 5 -C 5 H 5 )Co(CO) 2 (1) in tetrahydrofurane at -110°C. Although the yields of µ-dicarbonyl-µ-ethoxycarbonylmethylene- bis(ƞ 5 -cyclopentadienylcobalt) (3 a) and the corresponding ieri-butyl derivative (3b) are low, both compounds attract considerable attention due to an unexpected and hitherto unknown irreversible carbonyl bridge opening process with concomitant µ-methylene rearrangement. These isomerizations have been established by IR and 1 H NMR methods to be first order intramolecular processes.

Using a phosphoroscope and a pulsed light-signal integrator, the effect of alcohol on the delayed fluorescence of indole was investigated in alcohol-isopentane mixed glasses at 77 K. The delayed fluorescence intensity was strongly depended on the alcohol concen-tration and the polarity of alcohol. Trapped electrons causing the delayed fluorescence were separated into two species utilizing the scavenge effect of CCl 4 ; shallow trapped-electrons sensitive to CCl 4 and deep trapped-electrons insensitive to CCl 4 . The former electrons seem to be responsible for the delayed fluorescence at low alcohol concentrations, whereas the latter for the delayed fluorescence at higher alcohol concentrations. The delayed fluorescence decayed exponentially at low alcohol concentrations, but it decayed with the Debye-Edwards law of t -1 at higher alcohol concentrations. The recombination mechanism of trapped electrons with parent cations was discussed. The structure of shallow traps was also estimated.

A new furanoid diterpene of clerodane type, Montanin-D [1], is isolated from the bitter fraction of the arial parts of Teucrium montanum L., spread in Bulgaria. Its structure is established on the basis of spectral evidance and chemical transformations.

The oxazoline ring in 4-arylazo-2-aryl-2-oxazolin-5-ones (1) is converted to triazolyl-carbonyl amino acids 2, 4 and 6 by the nucleophiles glycine, anthranilic and p-aminobenzoic acids, respectively. The arylidene derivatives 3 of 2-triazolyl-2-oxazolin-5-one were obtained. Triazolylbenzoxazinones 5, were obtained by the ring closure of the amino acid 4. Grignard's reagent effected ring cleavage of the oxazolinone ring in 4-cinnamylidene-2-aryl-2-oxazolin-5-ones yielding the carbinols 8, the latter cyclizes either in acidic or alkaline medium to afford either benzotropilidenes or oxazolines, respectively.

The details of the elimination of CH 3 · and C 2 H 5 · from the molecular ions of n-butyl and n-pentyl benzenes as well as the formation of C 7 H 7 + and C 7 H 7 + -have been established using a combination of different mass spectrometric techniques. Among these techniques are field ionization kinetics (FIK), collisional activation (CA), unimolecular decomposi-tion of metastable ions (MI), kinetic energy release determinations (Tkin)> appearance potential measurements (AP) as well as high resolution mass spectrometry. The appli-cation of these methods and the investigation of nine 13 carbon and eleven deuterium labelled n-butyl and n-pentyl benzenes clearly demonstrate that 1) the loss of methyl and ethyl from terminal positions of the alkyl chains are accompanied by an interaction with the phenyl ring and 2) the regioselectivity of these processes is time dependent. Contrary to previous conclusions it is shown that hydrogen transfer in the formation of C 7 H 8 + -occurs via five-, six-and seven-membered transition states. The time dependence of the hydrogen exchange reaction preceding the alkene eliminations is discussed in detail.

The reactions of dialkyl t-butylperoxy phosphates (1) and alkyl t-butylperoxy alkylphosphonates (2) with cyclohexene in the presence of a catalytic amount of copper (I) bromide at 80 °C in benzene afforded the corresponding phosphates (3) and phosphonates (4) in 50 to 70% yield. The analogous reaction of 1 (R = i-C 3 H 7 ) with cycloheptene also gave the corresponding phosphate (8, n = 3) in 71% yield. However, phosphorylated cyclopentene (8, n = 1) and cyclooctene (8, n - 4) derivatives could not be isolated because of their thermal instability, and only the corresponding 1,3-cyclopentadiene and 1,3-cyclooctadiene were obtained in 92 and 38% yields, respectively. Thermal decomposition of 3 and 4 in the absence of a solvent at 110-115 °C gave 1,3-cyclohexadiene in 70 to 90% yield. For identification purposes, compounds 3 and 4 were prepared from the corresponding imidazole derivatives 5 and 6 and 2-cyelohexen- l-ol (7). A mechanism is proposed for the copper ion catalyzed reaction of 1 and 2 with cycloalkenes.

The photochemical reaction of dialkyl t-butylperoxy phosphates (1) and alkyl t-butylperoxy alkylphosphonates (2) with cyclohexene in benzene in the presence of a catalytic amount of copper (I) bromide produced the corresponding phosphates (3) and phosphonates (4) in 50-70% yield. The analogous reaction of 1 (R = i-C 3 H 7 ) with cyclopentene gave a 36% yield of cyclopent-l-en-3-yl di-isopropyl phosphate (5), which could not be obtained by the thermal copper ion catalyzed reaction. Benzene, benzophenone, and acetone were effective as triplet photosensitizers in the phosphorylation reaction. Typical free radical inhibitors, such as, galvinoxyl (6), 4-hydroxy- 2,2,6,6-tetramethylpiperidine-l-oxyl (7), and DPPH (8) retarded the photosensitized reaction. The reaction was not affected by the singlet sensitizer Eosin-Y.

Cs 2 TiS 3 , black single crystals, dark red transparent, a = 12.518, b = 9.036, c = 6.550 Å, Z = 4. [Cmc 2 1 , 4-circle-diffractometer 4° ≤ ω ≤ 30°, Mok a , R = 5.68, R w = 5,12%] is isotypic with Cs 2 PbO 3 , exhibiting Coord. Number 5 of Ti 4+ .

Tris(trimethylstannyl)phosphine reacts with methyllithium in ether forming tetramethyltin and bis (trimethylstannyl )lithiumphosphidemonoetherate in high yields. The Raman, 1 H and 31 P NMR spectra are reported and discussed. The compound does not form a stannylated diphosphine with 1,2-dibromoethane.

Disproportionation of monoorganothallium acetate RT1X 2 (X = CH 3 COO) does not become evident at room temperature since equilibrium concentrations of disproportionation products, R 2 TIX or TIX 3 are too small to be detected, e.g. by NMR spectroscopy (solvent: CD 3 COCD 3 / CH 3 OH; R = C 6 H 5 , CHs). (CH 3 O) 3 P, which had been used in the synthesis of Aryl 2 TlY (Y = CF 3 COO) from ArylTlYa [1], continuously removes TIX 3 from the equilibrium and effects disproportionation of ArylTlX 2 . In the same way disproportionation of an AlkylTlX 2 compound (Alkyl = CH 3 ) could be accomplished for the first time. The exchange of the organic groups is rate determining.

N - Salicylidene - D,L - valinato - thiourea - cop - per(U) complex reacts with thiourea to give magnetically diluted stable Cu(II) complex Cu(salal-D,L-val)(tu). This compound shows similar magnetic and spectral properties to those of N-salicyhdene-glycinato-thiourea-copper(II) complex [1].

N- (Dimethylaminosulfonyl)hydroxylamine is obtained from the reaction of dimethylaminosulfonyl chloride with hydroxylamine. This very weak acid has been characterized by IR, 1 H NMR, and mass spectra. The alkaline hydrolysis is reported.

Tetrakis-difluorooxosulfurimidato-metallates (II), [M(NSOF 2 ) 4 ] 2- , (M = Hg, Co, Pd) are prepared from Hg(NSOF 2 ) 2 , CoCl 2 and Pd(CH 3 COO) 2 , respectively, by reaction with (C 6 H 5 ) 4 PNSOF 2 or (C 6 H 5 ) 4 AsNSOF 2 .

Carbamate Salts, Catalytic Hydrogenolysis Catalytic hydrogenolysis of Z-Gly-NH 2 and Z-Ala-NH 2 resulted in the corresponding free amides and carbamate salts. This observation is a further experimental proof that carbamic acid derivatives are intermediates of hydrogen-olytic removal of carbobenzoxy group under neutral conditions. The ratio of the formation of the two compounds is dependent on the solvent, concentration and chemical structure. The carbamate salts can be acylated without difficulties under the conditions of peptide bond formation.

Thermal decomposition of S 6 O 2 and S 7 O, respectively, in CH 2 Cl 2 or CS 2 solution at temperatures between 20 and 5 °C yields SO 2 , polymeric sulfur and S 10 which was obtained as pure single crystals in yields of 7-11% with regard to the starting materials S 6 and S 7 , respectively. Infrared and Raman spectra of S 10 as well as of the new molecular addition compound S 6 · S 10 are reported.

Tetrahydroxy-benzoquinone-1.4, Tetraalkoxy-benzoquinones-1.4 Hydrolysis of easy available tetramethoxy-benzoquinone-1,4 leads to tetrahydroxy-benzo-quinone-1,4 in good yield. Tetramethoxy-benzo-quinone is obtained by a modified method from tetrachlorobenzoquinone. It is subsequently used for the synthesis of higher alkoxy-benzo-quinones-1,4.