Volume 34, Issue 2

Single crystals of CsAlF 4 have been prepared from a mixture of CsF and AlF 3 and investigated by X-ray methods, CsAlF 4 crystallizes hexagonally (isostructurally to the new CsCrF 4 -type) with a = 9.500, c= 3.713 Å, Z= 3, space group P62m-D 3h 3 , No. 189. AgAlF 4 crystallizes orthorhombically (isostructurally to a-RbFeF 4 ) with a = 7.108, b = 7.111, c = 5,568 Å, Z = 4.

The substituent exchange between trithiadiborolanes has been studied by the 10 B isotope technique. A simultaneous exchange of the substituent and the boron atom to which the substituent is bound was observed. This result is explained by a mechanism comprising a conformationally flexible ten membered ring as an intermediate. The exchange occurs not only between differently substituted trithiadiborolanes but also between trithiadiborolanes of one sort.

The title compound crystallizes in the monoclinic space group A 2/m (C 2h 3 ) with a = 10.61(3) Å, b = 9.511(5) Å and c = 16.47(5) Å, β = 124.2(1)° and two formula units in the unit cell. The structure was solved by Patterson and Fourier methods and refined by least squares to R = 0.071 based on 1251 observed intensities. The organic cations are slightly distorted and are arranged in dimers along the crystallographic a-axis. There are “mixed stacks” of the planar [Pt(CN) 4 ] 2− units which are separated from each other by the WB 2 2+ dimers along b. There is IR-evidence for the formation of hydrogen bridges between [Pt(CN) 4 ] 2− units and the crystal water during the modification change of the compound at room temperature.

The crystal structures of dicyclohexylammonium-monomolybdate dihydrate [(C 6 H 11 ) 2 NH 2 ] 2 MoO 4 · 2 H 2 O, (I), cyclohexylammonium-monomolybdate, (C 6 H 11 NH 3 ) 2 MoO 4 , (II) and tert-butylammonium-monotungstate, (C 4 H 9 NH 3 ) 2 WO 4 , (III), were elucidated. In I the anion has nearly tetrahedral structure, in II one Mo-O distance is significantly shorter than the other three, and in III all four W-O distances are different. In spite of the variety of structures the following basic principles are recognizable: 1) Each hydrogen atom of the cationic amino groups as well as of the water of crystallization forms hydrogen bridges. 2) Never are oxygen atoms of the same MoO 4 connected by these bridges, but always oxygen atoms of neighbouring MoO 4 units. 3) From an oxygen atom emanate either two or no hydrogen bridge. For the investigated molybdates (tungstates) there are in all instances isomorphous tungstates (molybdates). The number and position of the vibrational bands is in good agreement with the observed anion symmetry Td, C 3v and C 1 , respectively.

In the presence of small quantities of water MoO 3 is degradated by amines. In the process solvent free octa-, hepta-or monomolybdates are produced, or monomolybdates containing water of crystallization. The extent of the degradation is not dependent on the basicity of the amines but rather on the number of hydrogen-bridged bonds that the ammonium cation can form. The IR spectra indicate that the monomolybdates may be classified into 3 different structural types. In the reaction of monomolybdates with Te(OH) 6 , Ni(NO 3 ) 2 · 6 H 2 O or FeCl 3 · 6 H 2 O in methanol hexamolybdato-tellurate, niccolate or ferrate were obtained. The solubility of iso and heteropolymolybdates in organic solvents was investigated.

Chromium(III) Chloride, Basic Chromium(III) Formate, IR, Thermogravimetry, Magnetic Moment Chromium(III) chloride reacts with anhydrous formic acid to give basic chromium(III) formate [Cr 3 O(OOCH) 6 (H 2 O) 2 (HCOOH)](OOCH), HCOOH. Its reactions with bases (B) give compounds of the general composition [Cr30(C00CH)6(B)3](00CH). The title compound has been characterized by infrared spectral data, temperature range (266-110K) magnetic moment and thermogravimetry.

Tris-tert-butylorthovanadate VO(OC 4 H 9 ) 3 undergoes reaction with monocarboxylic acids to yield monomeric VO(OC 4 H 9 )(RCOO) 2 ; no VO(OC 4 H 9 ) 2 (RCOO) or VO(RCOO) 3 could be isolated from the reaction mixture. Polymeric dioxovanadium(V)-monocarbox-ylates(VO 2 RCOO) n are formed by thermolysis or partial hydrolysis of VO(OC 4 H 9 )(RCOO) 2 ; the reaction mechanism is studied and discussed. Syntheses of Ba[VO 2 (CH 3 COO) 3 ], Ba[VO 2 (C 2 H 5 COO) 3 ] and N(C 4 H 9 ) 4 [V 4 O 8 Br(CH 3 COO) 4 ] are described. All compounds obtained are characterized by IR and 1 H NMR spectroscopy as well as by chemical reactions. The carboxyl groups are mostly acting as bidentate ligands.

RbSb 3 S 5 · H 2 O has been prepared and its structure determined. The compound crystallizes triclinic, P1̄ with a = 1053.6(5) pm, b = 893.8(5) pm, c = 599.0(5) pm, α = 87.09(5)°, β = 100.33(5)° and γ = 102.39(5)°. SbS 4 -ψ-trigonal bipyramids and SbS 3 -ψ-tetrahedra are connected together to sheets separated by Rb-ions and water molecules.

Na 3 (AlSi)Te 4 has been prepared and analytically characterized. The compound is monoclinic, C2/m, with a = 747 ± 1 pm, b = 434 ± 1 pm, c = 852 ± 1 pm, β = 107.4° ±0.1. The structure can be described as a variant of the a-NaFeO 2 -type. One half of the octahedral sites is occupied by Na ions while in the other half of these holes Na ions and Al-Si-dumbbells in the ratio 1:1 are randomly distributed.

By substitution of chlorine in the title compound 2,2,4,4,6,6-hexachloro-3,5-dimethyl-4-bora-2,6-diphospha-1,3,5-triazene (1) new members of this class of compounds are synthesized. In most cases reaction starts first on the boron site. The ring reactivity can be accounted for in terms of the charge distribution in the heterocycle 1. In 1 the coupling 2 J( 31 P-N- 11 B) could be detected for the first time. A mechanism for the ring formation is discussed.

Conductometric measurements of the catalytic oxydation of dilute aqueous sulfurous acid were used in the comparison of various carbon catalysts, e.g. active charcoals and carbon blacks. The oxidation rate is proportional to (Po 2 ) 1/2 and to the amount of adsorbed HSO 3 - ions. Basic surface oxides are responsible for the HSO 3 -adsorption. The catalytic activity of a carbon is influenced also by other factors than the concentration of basic surface oxides. It is changed by heat treatment of the carbon as well as by chemical treatment of its surface. Treatment with ammonia at 600 °C increases its activity dramatically, absolutely inactive carbon blacks were rendered highly active.

The reactions of N,N′ -bis(pentafluorophenyl)sulfurdiimide with [(CH 3 ) 3 Sn] 2 NCH 3 , [(CH 3 )3Sn] 3 N and [(CH 3 ) 3 Sn] 2 NC 6 F 5 yiels the 1:1 adducts 1-3. 1 H and 19 F NMR investigations show, that fluorine atoms in the ortho position of the phenyl ring coordinate to the tin atom. This causes an increase of electron density at tin. A similar interpretation is given for the adduct 4 of N,N′-bis(p-chlorophenylsulfonyl)sulfurdiimide and [(CH 3 ) 3 Sn] 2 NCH 3 , where an oxygen atom of the sulfonyl group is bonded to tin.

The preparation and characterization of a series of azido chelate complexes of cobalt(III), N 3 Co(chel) 2 B (chel = anionic bidentate ligand, B = base e.g. PPh 3 , P(OEt) 3 ) and N 3 Co(chel′)B (chel′ = anionic tetradentate ligand) is reported. In addition, analogous chelate cobalt(III) complexes containing the pesudo halides NCO-, NCS -, CN -, C ≡ CR-, C(CN) 3 -, CH 2 NO 2 - have been prepared.

The stability constants of ternary Cu 2+ and Zn 2+ complexes, each of which contains 2,2′-bipyridyl and a carboxymethyl aryl sulfide, were determined in 50% aqueous dioxane. A comparison of the stability of these ternary complexes with those formed with simple carboxylates demonstrates an enhanced stability of the carboxymethyl aryl sulfide containing mixed ligand complexes. This enhanced stability is not due to a thioether-metal ion interaction, but due to an intramolecular aromatic stacking interaction between the aryl moiety of the carboxymethyl aryl sulfide and 2,2′-bipyridyl. Indeed, by UV difference spectra and by PMR measurements it is possible to show that a binary (metal ion-free) stacked adduct between the aromatic moieties of the two mentioned ligands is formed. Furthermore, by studying the binary and ternary systems of Zn 2+ or Cu 2+ , 2,2′-bipyridyl and hydrocinnamate, i.e. 3-phenylpropionate (-S-of carboxymethyl phenyl sulfide is replaced by -CH 2 -), it becomes obvious that the thioether moiety is not essential for the observation of an enhanced stability of the ternary complexes. PMR shift studies of 2,2′-bipyridyl/Zn 2+ /carboxymethyl aryl sulfide systems confirm the presence of stacking in the corresponding ternary complexes. Depending on the kind of the ternary metal ion complex the stability enhancement, due to the intramolecular stacking between the aromatic parts of the coordinated ligands, is between about 0.2 to 0.5 log unit.

The selenium bridged complexes [(CO) 4 M-SeX] 2 (M = Mn, Re; X = H, SnMe 3 ) were converted by trimethylphosphine to the dimers [Me 3 P(CO) 3 M-SeX] 2 and/or the monomers (Me 3 P) 2 (CO) 3 M-SeX. The obtained Se-SnMe 3 compounds reacted with HCl to form the SeH compounds. The structures of the new complexes were deduced from their IR and NMR spectra. [(Me 3 P) 2 (CO) 3 Re] 2 Se, the first monobridged bis-carbonylmetal chalcogenide, was obtained as a byproduct and confirmed by a crystal structure analysis.

Chemical oxidation of the mercapto carbonyl manganese complexes (Me 3 P) 2 (CO) 3 Mn-SX (1), (Me 3 P) 2 (CO) 5 Mn 2 (SX) 2 (2), and (CO) 8 Mn 2 (SX) 2 (3) (X = H, SnMe 3 ) were investigated. From the SH complexes no identifiable products could be obtained. For X = SnMe 3 , the iodine oxidation of 2 yielded (Me 3 P) 2 (CO) 5 Mn 2 S 2 (5), that of 3 gave (CO) 15 Mn 4 S 4 (7), both containing bridging disulfide ligands. The crystal structure of 7 was determined.

The reaction of nitrophenols (picric acid, 2,6-dinitrophenol, and 2,4-dinitrophenol) with divalent metal oxinate (metal = Cu, Co, Ni, Mn, and Zn) produced a type of molecular complex, which comprises two molecules of the metal oxinate and one molecule of the nitrophenol. In the case of the Mg complex the ratio is 1:1. A definite charge-transfer band is detected for the Co(II) complex. A hydrogen bonding system O 1 ...H+...O 2 is suggested. This includes the proton of the nitrophenol and two oxygen atoms; each is related to a coordinated oxinate of two different metal oxinate molecules. Analytical and spectral evidence are in accordance with the tentatively suggested formulations.

The assignment of some 13 C chemical shifts in 2-thienylstannanes has to be reversed. Proton coupled 119 Sn NMR spectra are shown to be useful to detect long range Sn-H coupling, not readily obtained from complex 1 H NMR spectra.

Metal-rich ternary chalcogenides M 3 M 2 ′X 2 (M = Ni, Co, Pd, Rh; M′ = In, Tl, Pb, Sn; X = S, Se) with Shandite-type structure were synthesized from mixtures of the elements and/or binary components. A single-crystal investigation on Co 3 ln 2 S 2 verifies the rhombohedral unit cell of Shandite-type compounds, originally postulated by Peacock and McAndrew (Crystal data for Co 3 ln 2 S 2 : Rhombohedral, space group R3̄m; a = 549,31 (6) pm, a = 57.89°, Z= 1; 3 Co in 3d, 1 In(l) in 1 a, 1 In(2) in 1 b, 2 S in 2c with x = 0.2790).

Depending on the pH and the respective concentrations of solutions containing NH 4 +/NH 3 /H 2 O 2 /NH 4 VO 3 three yellow ammonium salts can be isolated: (NH 4 ) 4 [O(VO(O 2 ) 2 ) 2 ], NH 4 [VO(O 2 ) 2 NH 3 ]; and the novel (NH 4 ) 3 [HV 2 O 11 ] · 2 H 2 O. A cesium and potassium salt of the latter anion have been prepared. The infrared spectra of these salts are interpreted assuming a μ-hydroxo-bis[oxo-diperoxovanadate(V)] structure in the solid state.

A series of new planar bis(α,β-dionedioximato) metal(II) complexes of the ions Ni(II), Pd(II), Pt(II)using unsymmetrically substituted glyoximes as ligands are reported. Typical ligands being unsymmetrically substituted benzildioximes, phenylglyoxime or butan-1,2-dionedioxime.The solid state properties and in some cases the X-ray data suggest, that most of the isolated complexes crystallize in columnar stacks. Compared with the known symmetrical derivatives the solubility of the isolated neutral compounds in organic solvents like ethanol, chloroform or 1,2-dichlorobenzene is highly increased. Most of the compounds can therefore be obtained in good crystalline form. The good solubility is an advantage in the efforts to extend the polarizable ligand system of the complexes.

SrZnSb 2 has been prepared and characterized analytically and structurally. The compound crystallizes in the orthorhombic system with a = 2305 ± 5 pm, b = 437 ± 1 pm, c = 446 ± 1 pm, Pnma-D 2h 16 . Zn- and Sb-atoms form distorted fourfold pyramids, connected by common edges in the basis to two-dimensional sheets. These sheets are separated by double layers of Sr-atoms in which further Sb-atoms are located building four-cornered networks.

The crystal structures of the compounds [R 3 CP(X)NR] 2 (R= CH 3 ; X=S, Te for cis isomers and X= lone pair, S, Te for trans isomers) (2-6) were determined from single crystal X-ray data. The four-membered P-N rings in the cis isomers 2 and 3 show significant deviations from planarity attributed to steric overcrowding in the molecules.The trans isomers 4-6 are planar. The P-N bond lenghts (mean values for 2-6:171.4, 170, 171.6, 169.2 and 168.3 pm)in the cis isomers are not significantly different from the corresponding lengths in the trans isomers 5 and 6.

The preparation and the electronic spectral properties of compounds M[Al(OR) 4 ] 2 (M = Co, Ni, Cu and R = CH 3 , C 2 H 5 , n-C 3 H 7 , n-C 4 H 9 ) are described. The spectral data are used in conjunction with ligand field theory in deducing the structures of the compounds. The spectrum of green Ni[Al(OR) 4 ] 2 is interpreted as a Ni(OR) 6 octahedron sharing faces with two Al(OR) 4 tetrahedrons. It is proposed that Co 2+ and Cu 2+ are in a distorted octahedral coordination. The alkoxide ligands have been fitted into the spectrochemical and the nephelauxetic series. They are close to H 2 O in this series.

The electronic spectra of a series of substituted 4-hydroxypyridones are calculated by the CNDO/CI-method. Best agreement between observed and calculated transition energies is obtained when the geometry of the pyridone-form is assumed. In addition, MINDO/2-calculations predict the pyridone tautomer to be the more stable one in most cases.

The irradiation (λ = 313 nm) of aqueous [Co(III)(NH 3 ) 5 TSC] 2+ (TSC-= trans-4-stilbenecarboxylate) leads to a redox reaction with formation of Co 2+ as has been shown previously. The TSC-ligand is oxidized to the radical in the primary photoreaction. At higher complex concentrations (～10 -2 M) this TSC radical is oxidized to stable products (Φ = 0.09 ± 0.02) by [Co(NH 3 ) 5 TSC] 2+ ,which is reduced to Co 2+ leading to release of the TSC- ligand (Φ = 0.07 ± 0.02). Co 2+ is thus formed by both the secondary and the primary photo chemical reaction (Φ overall = 0.16). At low complex concentrations (< 10 -4 M) in the presence of air, the primary TSC radical is scavenged by O 2 . Benz-aldehyde is an oxidation product. This reduces the formation of Co 2+ to Φ = 0.09 ± 0.02, which is taken to be the efficiency of the primary photo chemical step. It is suggested that the photoredox reaction is initiated by an electron transfer from the first excited singlet of the TSC- ligand. As shown by sensitization experiments, the population of the lowest TSC-triplet leads to the usual trans/cis isomerization of the TSC-ligand, but not to the redox reaction.

Diazotised 5-amino-3-hydroxy-4-phenylazopyrazole (1 a) and 3,5-diamino-4-phenylazo-pyrazole(1 b) coupled with active methylene reagents to yield the pyrazolo[1,5-c]-as-triazine derivatives (3a, b-5 a, b). On the other hand coupling of diazotised 1 a, with β-naphthal has afforded the acyclic azo derivative(6). Whereas diazotised 1 a underwent intramolecular cyclisation into the pyrazolo[1,5-c]-1,2,3,4-tetrazine derivative (3)on attemptet addition to acrylonitrile, diazotised 1 b reacted with acrylonitrile under the same conditions to yield the pyrazolo[1,5-c]-pyridazine derivative (4). Compounds 1 a, b reacted with benzoylisothiocyanate to yield the pyrazol-5-ylthiourea derivatives (10 a, b). Where as 10 a readily cyclised into the pyrazolo[3,4-c]-as-triazine derivative (11) on refluxing with pyridine, compound 10 b hydrolysed under the same conditions into the pyrazol-5-ylthiourea derivative (12).

An improvement of the synthesis of aminomalononitrile (2) can be achieved by using Raney-catalysts for the reduction of oximinimalonitrile at a H 2 -pressure of 4 atm and 20 °C. Due to the reactivity of oximinomalonitrile some new derivatives of oximinocyanoacetamide are obtained by O-and N-acylation. Condensation of 2 with benzilmonoxime leads to 2-amino-5,6-diphenyl-pyrazine-carbonitrile, with N-phenyl-formamidate 2-amino-2,2-dicyano-1-(N-phenylimino)-acetaldehyde (10) is yielded. Oximinomalonitrile, Aminomalononitrile, Oximinocyanoacetamide

Three component condensation of active methylene compounds with aniline and trialkyl orthoformate gives anilinomethylene-1,3-dicarbonyls, which can be hydrolysed with aqueous K 2 CO 3 , KOH or HCl, depending on the sensitivity of the hydroxymethylene derivative thus formed. The reactions sequence is fairly generally applicable: Cyclohexan-1,3-diones, pyrimin-3,5-diones (including barbituric acids), pyrazolones and pyrazolin-3,5-diones, indan-1,3-dione, (thio)phthalide, indoxyl, oxindole, anthrone, 2,6- and 2,7-dihydroxynaphthalene, and pentan-2,4-dione have been formylated. Using orthoacetate or orthopropionate, tetronic acid, pyrazolones and pyrazolin-3,5-diones,resp.,could also be acylated by this method.

A supposed benzoxete is determined as a complex polycyclic system: cis,cis,cis-5 aH,10 aH,15 aH-tribenzo[b,f,j][1,4,7]trioxa[9 b]azaplienalene. The structure elucidation is performed by spectroscopycal methods (IR, 1 H NMR, 13 C NMR and mass spectroscopy) and by degradation reactions in an acidic or an alkaline medium.

The examples of cyclodiphosphazanes so far studied do not contain any nuclei of biological interest [1]. In the present investigation we aimed to introduce ethyl p-amino-benzoate, 2-aminopyridine residues in the phosphazane molecule. For this purpose phosphorus pentachloride was treated with ethyl p-aminobenzoate, p-anisidine, 2-amino-pyridine and 5-aminoquinoline to give 1,3-di-p-ethoxycarbonylphenyl-, 1,3-di-p-methoxy-phenyl-, 1,3-di-2-pyridyl-and 1,3-di-5-quinolinyl-2,2,2,4,4,4-hexachlorocyclo-diphos-phazane (1 a-d), respectively. The compounds 1 a-d were treated with potassium thio-cyanate in acetone. The oily products formed were then treated with p-anisidine, ethyl-p-aminobenzoate and 2-aminopyridine whereupon solid products (2 a-h) were obtained. The reaction probably takes place according to the following mechanism [2].

By examining suitably substituted analogs of carotenoids the steric and electronic influences governing the elimination of xylene and toluene from the polyene chain have been clarified.

Starting from 4-methylpyridine a 3-aza-Δ 8 -tetrahydrocannabinol-analogous (2d) was prepared. The reaction sequence also includes the first synthesis of a 6 H-benzo(4,5)-pyrano(2,3-c)-pyridin-6-on, a novel ring-system. The proposed structures were supported by spectroscopic data ( 1 H NMR, IR, MS).

3-n-Heptyl- and 3-n-nonyl-3-hydroxy-1, 2, 3, 4-tetrahydroquinoline-2,4-dione have been isolated from the culture medium of Pseudomonas aeruginosa. Their structures have been elucidated.

It is shown for the first time that under electron impact conditions an intramolecular oxygen transfer is possible from the thiol ester funtion onto the carbon atom of a second thiol ester group. The reaction sequence is terminated by CO 2 elimination and the proposed structure of the resulting product ion is based on 13 carbon labelling experiments and collisional activation mass spectrometry. In addition, some unusual examples of ring contraction processes in the gas phase are reported.

Three models of alkyl groups, “derealization”, “through-the-bond”, and “electric field” models, are presented, all of which enable the calculation of σ I (R) from first principles, and excellent agreement is demonstrated for the calculated and experimental values of σ I (R) . For the “delocalization” model it is found that - σ I (R) = 0.0455 + 0.0232(1-1/n), where n is the number of C atoms in an n-alkyl group, and for an infinite C-chain R group, σ I ( R ∞ ) is - 0.0687, identical to the value found b y a different method in Part I of this series. The “through-the-bond” model gives - σ I (R) = - 0.0559 +, where C i is the number of C-atoms in the i th position from X in RX; and for the “electric field” model, we obtain - σ I (R) = 0.0463 + 0.0102 , where d i is the calculated distance from C 1 to C n in the most probable conformation of the R-group. It is concluded that Taft's σ I (R) values have a real significance whether or not the physical and chemical effects of alkyl substitution reside ultimately in an internal induction mechanism, or in alkyl group polarization by charged centers in the molecule, or a combination of the two.

The main products in the 185 nm photolysis of neat 1,4-dioxane are formaldehyde (Φ = 0.25), glycol monovinyl ether (0.17), and ethylene (0.15). Some hydrogen (0.04), carbon monoxide (0.01), acetaldehyde (0.03), oxetane (0.04), and bidioxanyl (0.01) are also formed. On N 2 O-saturation, the quantum yields of these products are diminished by about 30%, and N 2 (0.59) and hydroxydioxane (0.4) become the main products. They are thought to be formed in the reaction sequence In aqueous dioxane, photoionisation is possible due to a greater lowering of the ionisation threshold. In dioxane/water 20:80 the main products are H 2 (0.50) and bidioxanyl (0.45), most likely formed in consequence of

The tautomeric equilibria of 4,7-dioxo-4,5,6,7-tetrahydroindoles have been investigated by nuclear magnetic resonance spectroscopy. Proton chemical shift measurements have been made for a series of alkyl or arylindole derivatives, and equilibrium constants ([enol]/[keto]) have been determined. The effect of solvent on the enol-keto equilibria has been studied.

The oxidation reaction of singlet oxygen with 1,3-diphenylisobenzofuran was investigated in cyclohexanic reversed micellar solutions of dodecylammonium propionate, using pyrene as photosensitizer. The furan oxidation was effectively inhibited by azide ion-bound reversed micelles. Empty reversed micelles also inhibited the furan oxidation to some extent. The inhibition of the furan oxidation was due to the quenching of singlet oxygen by azide ion-bound and empty reversed micelles. Such singlet oxygen quenching was dependent on the concentration of water added. Results obtained were discussed in connection with the polarity in the interior of reversed micelles, micellar size, the state of water solubilized in reversed micelles and the lifetime of singlet oxygen. The heavy atom effect on the quenching of singlet oxygen was also studied using heavy water.

The effect of LiCl on the delayed luminescence caused by the recombination of photo -ejected electrons with tryptophan cations in aqueous solutions was investigated at 77 K. The luminescence intensity strongly depended on LiCl concentration. At high LiCl concentrations, the intensity of the fast decay component of the recombination fluorescence decreased to a constant value, whereas that of the slow decay component inversely increased. The intensity of the recombination phosphorescence was weak and unchanged in low LiCl concentration range but increased steeply above 7 M LiCl. NO 3̄ , electron scavenger, quenched both the recombination fluorescence and phosphorescence, but the degree of the quenching decreased rapidly in the order of the fast decay component of the recombination fluorescence, the slow decay component of the recombination fluorescence, the recombination phosphorescence. Furthermore, the quenching efficiency of NO 3̄ for each recombination luminescence was found to diminish with increasing LiCl concentration. The distribution of photo-ejected electrons to shallow-and deep-traps, dependent on LiCl concentration, was discussed from results obtained.

The new compounds MgBe 2 P 2 , MgBe 2 As 2 , CaBe 2 P 2 and CaBe 2 As 2 have been prepared. They are supposed to crystallize trigonally in a CaAl 2 Si 2 -type structure.

The intermetallic compounds NaAlSi and NaAlGe have been prepared and their structure has been determined by powder data. They crystallize in an anti-PbFCl-type lattice with the following cell dimensions: NaAlSi: a = 413.5 pm, c = 737.9 pm, c/a = 1.78 5 ; NaAlGe: a = 416.4 pm, c = 742.7 pm, c/a = 1.78 4 .

Na 2 AgSb crystallizes orthorhombically, space group Cmcm, with a = 929.2 pm, b = 790.3 pm, c = 577.3 pm. The structure contains Ag-Sb-zigzag-chains with ∢ Ag-Sb-Ag = 180° and ∢ Sb-Ag-Sb = 64.9°.

The acid-catalyzed decomposition of diazene, formed as an intermediate by the reaction of bis(trimethylsilyl)diazene with acids, leads by dimerisation via tetrazene to ammonium azide.

Corrugated Si-layers in trigonal Ca 0,65 Sr 0,35 Si 2 (EuGe 2 type of structure, D 3d 3 -P 3̄m l, a = 389.1 pm, c = 504.8 pm, Z = 1, z Si = 0,420) are transformed by a high pressure-high temperature treatment into a tetragonal three-dimensional Si-network (a = ThSi 2 type of structure, D 4h 19 -I 4 1 /amd, a = 433.6 pm, c = 1367 pm, Z = 4, z Si = 0.414).

The unit cell of Ag 7 GeS 5 I, a member of the argyrodite family, is cubic face-centered with a = 1072.2(7) pm and Z = 4. The anion lattice consists of three-dimensionally connected Frank-Kasper polyhedra with C. N. 12 and 16. The silver ions are statistically distributed over a number of sites with C. N. 4, 3 and 2, formed by isolated GeS 4 -tetrahedra, as well as isolated S 2− - and I − -ions.

The UV-behaviour of some chlorinated tri-cyclic dienes (1 a-e) was studied in acetone. Cycloaddition (2 a-b and 2 d-e), hydrogen-transfer (3 c′ and 3 d) and photo ene-(3 c)-reaction products could be isolated and identified with the help of spectroscopic methods.

For possible molluscicidal activity, 1-(4- quinolyl)-2-nitro ethylenes, 1-(4-quinolyl)-2- methyl-2-nitro ethylenes, 2-styryl, and 2- (p-nitro styryl)-quinolines were synthesized.

Malonamide reacts with antimony(V)chlorid to a 1:2-adduct (1) at roomtemperature. By heating this complex dichloromalonamide (2) was formed; hydrolysis of the complex yields a new heterocycle with the composition C 3 H 4 Cl 5 N 2 O 2 Sb (3).