Volume 30, Issue 5-6

Methyl azide reacts with nitrosyl hexachloroantimonate(V) according to the conditions to yield nitrogen, dinitrogen oxide and methyl chloride or N-methylmethylenimonium hexachloroantimonate(V) (1). Independant of the conditions ethyl or isopropyl azide give 1:1-compounds of the azides with antimony(V) chloride and ethylidene or isopropylideneimonium hexachloroantimonate(V) (2) or (8).

Chromates and polychromates with organic cations can be obtained by careful hydrolysis of mono-, di- or trichromate esters in the presence of organic bases. Mixtures of nitrobenzene and carbon tetrachloride are used as solvents. When nitrobenzene soluble chromates are reacted with chromate esters more condensed anions such as tri- and tetrachromates are formed. As tetra-n-butylammoniumsalt [(C 4 H 9 ) 4 N] 2 Cr 3 O 10 for the first time a trichromate was obtained that can be recrystallized undecomposed from water.

The results of X-ray structure determinations on single crystals of KTlF 4 are reported. The unit cell is trigonal with α = 8.025, c = 10.16 A, Z = 6; space group: P 3 1 - C 2 3 . KTlF 4 is a new superstructure variant of the CaF 2 -type. Each Tl is coordinated by 7, K by 8 resp. 9 F. Other A+B 3 +F 4 -type compounds (A+ = Na, Ag, K; B 3+ = In, Tl, Ln) are isostructural with KTlF 4 .

A new lithium germanide Li 11 Ge 6 has been found and its crystal structure has been determined. It crystallizes orthorhombic, α = 4.38 ± 0.01 Å, b = 24.55 ± 0.05 A, c = 10.64 ± 0.02 Å, space group Cmcm-D 2h 17 . The Ge-sublattice consists of isolated, plane, five-membered rings and isolated atoms.

A new compound Li 13 Sn 5 has been prepared and its crystal structure has been determined, It crystallizes trigonal, α = 4.70 ± 0.01 Å, c = 17.12 ± 0.04 Å, c/α = 0.2745, space group P3̅ml-D 3 3d , in an ordered bcc derivative structure. Structural relations to other compounds of the systems Li—Sn and Li—Pb with similar atomic arrangements are shown. The Sn—Sn and Pb—Pb-distances are discussed in connection with the valence rule 18 .

By reaction with NaN[Si(CH 3 ) 3 ] 2 , the chlorides C 6 F 5 SCl, C 6 F 5 S(O)Cl, and C 6 F 5 SO 2 Cl are converted into C 6 F 5 SN[Si(CH 3 ) 3 ] 2 , C 6 F 5 S(O)N[Si(CH 3 ) 3 ] 2 , and Na + [C 6 F 5 SO 2 ] - , respectively. In this instance the reactivity pattern of the pentafluorophenyl compounds does not differ from that of similar phenyl derivatives.

The phosphorylhalides OPF 2 Cl, OPFCl 2 and OPCl 3 react with Ag+NS(O)F 2 - (1) to yield the phosphorylsulfuroxidedifluorideimides (2)—(7). Reaction of SPCl 3 and 1 yields the thiophosphorylhalides SPCl 3-n (NSOF 2 ) n , and by decomposition of 11 SPF(NSOF 2 ) 2 is formed. The IR, mass, 1 H, 19 F and 31 P NMR spectra of the above mentioned compounds are reported.

It was shown by cyclovoltammetry that carbon-monoxide dissolved in organic electrolyte can be reduced irreversibly at Ni-, Co-, and Ti-electrodes. A dependance of the potential on the metal was evident, corresponding to chemisorption and subsequent reduction of CO.

Yellow phosphatovanadates M 2 O · V 2 O 5 · P 2 O 5 · H 2 O (M = K, Rb, Cs, NH 4 ), 2 K 2 O · V 2 O 5 · P 2 O 5 and M 2 O · 2 V 2 O 5 · P 2 O 5 · aq (M = K, Rb, NH 4 ) are prepared; their properties studied by chemical reactions, 1 H NMR and IR spectroscopy indicate a polymeric constitution of these compounds. No polyphosphatovanadic acid can be isolated; condensation reactions in highly acidified sodium metavanadate solutions, containing an excess of sodium dihydrogenphosphate, yield polymeric oxide hydrate VPO 5 · 2 H 2 O.

The ‘broad single line’ at —127 ppm (from 85% H 3 PO 4 ), reported in the literature for the 31 P NMR spectrum of α-P 4 S 3 J 2 , could be resolved into 10 lines which form together with also detected outer signals of low intensity an AA′BB′ system with 24 observable lines. Therefore, α-P 4 S 3 J 2 has the same bicyclic molecular structure 1 in solution as in the solid state. The chemical shifts of the atoms PA and PB, determined by analysis of the spectrum, have the very small difference of 3.68 ppm, which may be caused by an accidental compensation of substituent and ring tension effects. The infrared spectrum of α-P 4 S 3 J 2 is consistent with formula 1 too.

The study of a series of arsine boranes reveal that (C 6 H 5 ) 3 As is a stronger base than (C 6 H 5 ) 2 AsH and that the Lewis acidity of some boranes towards these bases decreases in the series BBr 3 > BH 3 > CH 3 BBr 2 > (CH 3 ) 2 BBr > (CH 3 ) 2 BSCH 3 . The borane adducts of (CH 3 ) 4 As 2 , (CH 3 ) 3 SiAs(C 6 H 5 ) 2 , (CH 3 ) 3 SiAs(CH 3 ) 2 and (CH 3 ) 3 SnAs(CH 3 ) 2 are thermally unstable. (CH 3 ) 3 SiAs(C 6 H 5 ) 2 · BBr(C 6 H 5 ) 2 yields (CH 3 ) 3 SiBr, B(C 6 H 5 ) 3 and [AsC 6 H 5 ] n on decomposition.

The reduction of Zn(II) at the d.m.e. has been studied in aqueous mixtures of formamide and dimethylformamide. The general polarographic characteristics have been determined, using 0.1 M NaNO 3 as the supporting electrolyte. The reduction of Zn(II) in these organic solvents is irreversible and diffusion controlled. The kinetic parameters, αn a and k f,h have been calculated separately by KOTECKY and DELAHAY treatments. The change of polarographic characteristics and kinetic parameters is explained in terms of solvation of the metal ion in these solvents. The electrocapillary curves in the presence of these solvents have also been studied.

Upon ligand field excitation (300 nm-370 nm irradiating wavelengths) aqueous Fe(CN) 5 CO 3- underwent a photosubstitution under release of CO and formation of Fe(CN) 5 H 2 O 3- with the quantum yield 0.9.

The spectrophotometric titration of three-step sequential dissociation equilibria is analyzed by means of two dimensional absorbance diagrams. The evaluation of pK 1 and pK 3 as well as of the absorbance coefficients of both ampholytes is made by the uniform segments at the beginning and end of the titration. New methods of evaluating the value of pK 2 precisely and without difficulty even at small pK-differences are described. By means of several independent criteria the pK-values and the absorbance coefficients of the ampholytes can be examined. The titration of (1,2,4)-benzenetricarboxylic acid illustrates the new method.

Hexachloro-bicycloheptenes and heptadienes with hydroxymethyl-substituents in the 2 and 3 position show non-equivalence of the methylene protons in their NMR spectra. This is caused both by hindered rotation and the asymmetry of the molecules. For some molecules the spectroscopic data allow conclusions to be made concerning the conformation of the substituents.

The phosphide bromides M 2 PBr with M = Ca, Sr, Ba were prepared by reaction of metal, red phosphorous, and metal bromide corresponding a molar ratio M : P : Br = 2 : 1 : 1. In the systems “Ca 3 P 2 ”–CaBr 2 and “Sr 3 P 2 ”–SrBr 2 phase analytical investigations were made by varying the molar ratio M :P : Br. A cubic and a rhombohedral Ca 2 PBr- and Sr 2 PBr-phase as well as rhombohedral Ba 2 PBr were obtained. The cubic phases are stabilized by an excess of MBr 2 , the rhombohedral phases of Ca 2 PBr and Sr 2 PBr by an excess of “M 3 P 2 ” beyond the molar ratio 2:1:1. Analytical results, densities and lattice constants of the phases are given.

An air-stable porphodimethene, namely α, γ-dimethyl-α, γ-dihydrooctaethylporphyrin [H 2 (OÄPMe 2 )*; (1)] is metalated with Fe(CO) 5 /I 2 in toluene to yield an air-stable binuclear iron(III) porphodimethene, μ-oxobis(α, γ-dimethyl-α, γ-dihydrooctaethylporphinato)iron-(III) [(OÄPMe 2 )FeOFe(OÄPMe 2 ); (2a)] after chromatography and crystallization. 2a is transformed into the mononuclear hemins Fe(OÄPMe 2 )X [X = OMe, OPh, OAc, Cl (2 b-2 e)] and into a nitrosyl heme Fe(OÄPMe 2 )NO (2f). Other hemes are identified in solution. The compounds are characterized by elemental analyses, electronic-, IR, and mass spectra. IR data and magnetic moments as measured in solution by the Evans method allow a distinction between the mononuclear and binuclear species. While the Fe II porphodimethenes (hemes) show only one strong absorption in the visible region λ≈460 nm; like Zn(OÄPMe 2 ), the Fe III species (hemins) have three characteristic strong bands (λ≈ 400, 450, and 540 nm for the μ-oxo species).

In aqueous solutions the nonelectrolyte [Co(DH) 2 (NO 2 )(H 2 O)] participates in protolytic eqilibria and thus it exists in 7 different forms. Rate constants of the aquation, which leads to the substitution of the nitro group, have been measured in the pH-range between 3.72 and 8 at various temperatures. From these data rate constants, activation energies and entropy values of the aquation of 2 ionic species have been derived, as well as equilibrium constants for the protolytic equilibrium between these species. The kinetic parameters obtained have been compared to those of the aquation of the ionic species which exist in acid and basic solutions and the correlation between structure and activation energy of the aquation has been discussed.

The main products of the 185 nm photolysis of liquid methyl n-propyl ether (quantum yields in parentheses) are n-propanol (0.70), methane (0.29), sec-butyl methyl ether (0.20), methanol (0.16), propionaldehyde (0.13), 3,4-dimethoxyhexane (0.09), ethane (0.08), and ethyl n-propyl ether (0.08). The quantum yields of further 24 minor products have been measured. The quantum yield of the sum of primary photochemical processes, the main ones of which are the homolytic scissions of the C–O bonds (reactions i and ii), is close to unity. Reaction (i) is favoured over reaction (ii) by nearly a factor of five. The elimination of molecular methane (iii) is the only other process of importance. C–H and C–C bond splitting is marginal.

The synthesis of methyl-phenylcyclopropenone (1 a) is decribed. Bromination of this and of diphenylcyclopropenone yields saltlike complexes 2 which are in equilibrium with their components. Di-n-propylcyclopropenone and bromine give the ring opened product 3d. la and N-bromosuccinimid give 4 and 5, phenyl brominated derivatives, in sulfuric acid. With cupric bromide substituted β-bromoacrylic acids are formed along with cyclopropenone dimers (7).

The rates of oxidation of four chelating agents with Ce(IV) in HClO 4 solutions, have been studied by the stopped-flow technique. The rates first increase with increasing acidity, reach maxima which are characteristic of the chelating agent and the medium, then progressively decrease with further increasing acid concentration. At their maximum reactivities, the tendencies for oxidation decrease in the following order: trans-1,2-diaminocyclohexane tetraacetic acid (CDTA) > ethylenedinitrilotetraacetic acid (EDTA) > diethylenetriaminepentaacetic acid (DTPA) > nitrilotriacetic acid (NTA). A mechanism for the oxidation of EDTA, involving Ce 4+ and Ce(OH) 8+ and both unprotonated and monoprotonated chelating agent, is proposed.

In the γ-radiolysis of deoxygenated N 2 O-saturated aqueous solutions of D-glucose (10 -2 M, 1 · 10 19 - 4 · 10 19 eV/g, dose rate 4.3 · 10 18 eV/g · h at 25°C), the following products have been identified: Gluconic acid (1), 2-deoxy-gluconic acid (2), arabinose (3), 2-deoxy-ribose (4), 5-deoxy-gluconic acid (5), glucosone (6), 3-deoxy-glucosone (7), 3-keto-glucose (8), [2-deoxy-3-keto-glucose (9), 4-deoxy-3-keto-glucose (10)] 3 , 4-ketoglucose (11), 3-deoxy-4-keto-glucose (12), 5-deoxy-4-keto-glucose (13), 5-keto-glucose (14), 2-deoxy-5-keto-glucose (15), 4-deoxy-5-keto-glucose (16), 6-deoxy-5-keto-glucose (17), gluco-hexodialdose (18), 5-deoxy-xylo-hexodialdose (19), ribose (20), xylose (21), erythrose (22), threose (23), 3-deoxy-pentulose (24), 2-butanone-(1,4)-diol (25), and dihydroxyacetone (26). G-values were also determined. In the primary processes OH radicals and H atoms from the radiolysis of the solvent water abstract carbon bound hydrogen atoms from D-glucose to give all six possible primary glucosyl radicals. The observed products are formed in disproportionation reactions of the primary glucosyl radicals (1, 6, 8, 11, 14, 18) or of sugar radicals which originate from the primary glucosyl radicals by water elimination (2, 4, 7, 9, 10, 12, 13, 15, 16, 17, 19), rearrangements (5, 14, 15), or loss of carbon monoxide (3, 4, 20). Products 1-5 and probably 20 have primary glucosyl radicals with the odd electron at C-1 as precursors. Radicals with the free spin at C-2 give rise to the products 6 and 7. Attack at C-3 yield products 8-10, at C-4 products 11-13, at C-5 products 14-17, and an attack at C-6 products 18 and 19. Products 21-26 are formed in very low yields and hence are of minor importance. Their mechanism of formation has not been investigated.

Syntheses of 2,3-dihydro-3-methoxyfuro(2,3-b)quinolines starting from the respective 3-vinyl-2-quinolones are described.

The spatial disposition of a 2-methylthio group in the 4-methyl-1,3,2-dioxaphosphorinanyl ring system was studied by stereochemical correlation, 1 H, 13 C and 81 P NM-R. It has been established that a CH 3 S-group prefers an axial orientation much more strongly than does a methoxy group.

Reaction of 2-acetoxy-cyclohexa-3,5-dienones (“quinol-acetates”) with BF 3 or (CH 3 CO) 2 O/BF 3 in the presence of benzene derivatives (mesitylene, mesitol, 1,3-dimethoxybenzene, 1,3,5-trimethoxybenzene) yields biphenyl and diphenyl methane derivatives. The reasons for their formation are discussed.

The arylidene derivatives (1) of 1,3-thiazolidine-2,4-dithione undergo 1,4-cycloaddition reaction with acrylonitrile, ethyl acrylate, ω-nitrostyrene, styryl ethyl ketone and N-aryl-maleimides leading to substituted tetrahydrothiopyrano-7 H[2,3-d]thiazole-2thiones (2), (8) and (4). Grignard reagents effects addition to the double bond of the lateral chain of 1 to yield products proved to have structure 7.

With a simple mathematical method the three-component-system eH 3 Ci (citric acid) + fAlCI 3 + gNaOH was analysed and the formation of complexes between citrate and aluminium calculated. Mixtures of eH 3 Ci + fAlCI 3 , with e/f ratios from 0 to 2.5 were titrated with NaOH. For each titrated mixture which existed of eH 3 Ci + fAlCI 3 the coefficient g(NaOH) was found from the inflection points of the titration curves. When the eH 3 Ci/fAlCI 3 molar ratios were plotted against the corresponding molar ratios of gNaOH/fAlCI 3 , linear functions were obtained from which the following three dehydrated complexes were calculated : [Al 3 OHCi 3 ] ⊖ from the first inflection point at pH between 3.0-3.5, [Al 3 (OH) 4 Ci 2 ] ⊖ from the 2nd inflection point at pH between 3.8-4.8, and [Al 10 (OH) 15 Ci 6 ] 3⊖ from the 3rd inflection point at pH between 5.6-7.5.

Powder susceptibilities in the temperature range 4.2 to 295°K are reported for the antiferromagnetic compounds ACrF 4 (A=Na, K, Rb, Cs, Tl) and K 2 Cr 5 F 17 .

The matrix isolation spectrum of germanium tetrachloride in the region of the v 3 (F 2 ) vibration has been measured. Applying the isotopic substitution technique the spectrum of the normal sample could be interpreted. The frequencies of the different isotopic species have been assigned.

NSF 3 reacts with OSF 4 to give F 5 S-NSOF 2 which hydrolyses with alkali to the ion [F 5 S-NSO 2 F]-. From NSF 2 -N(CH 3 ) 2 and SF 4 or OSF 4 only F 5 S-N(CH 3 ) 2 is received together with decomposition products NSF resp. (NSOF) 3 .

The parameters of complete X-ray structure determinations are given for the fluorides Rb 2 NaFeF 6 and Rb 2 KFeF 6 (cubic), Cs 2 NaCrF 6 and Cs 2 NaFeF 6 (hexagonal-rhom-bohedral) and Cs 2 LiGaF 6 (hexagonal). Space group and lattice constants of the monoclinic cyanides Cs 2 BFe(CN) 6 (B = Na, K, Rb) are reported as well.

Nitrogen tribromide was prepared andisolated in a pure state. Its analysis and molecular spectra are reported briefly. Reactions with ammonia, tertiary organic Nbases, and iodine give monobromamine, molecular addition compounds between Nbaseand bromine, and nitrogendibromidemonoiodide,respectively.

A hydrogenation catalyst, operating under mild conditions can be prepared by dissolving H 2 PtCl 6 and SnCl 2 · 2 H 2 O in acetic acid. After injection of an unsaturated compound under a H 2 -atmosphere the active moiety of the catalyst is generated. No active moiety of catalyst is formed if the compound has a triple bond. But acetylenic derivatives are hydrogenated if the active moiety of the catalyst is first produced by hydrogenation of cyclohexene.

By reaction of NiCl 2 or NiCl 2 · 6 H 2 O with NaBH 4 in dimethylformamide an active hydrogenation catalyst, working under mild conditions is produced. Methods for preparation of catalyst, using acrylicethylester as an unsaturated compound are described. Reaction rates r up to 26 (mMol · I —1 ·ܨ min —1 ) were found.