Band 30, Heft 3-4

MnIn 2 Te 4 was prepared by direct synthesis from the elements at 800°C. The crystals are tetragonal, space group I 4̅ 2 m, with a = 6.191 Å, c = 12.382 Å, and Z = 2. The structure can be derived from the zincblende structure. It is related to the CdGa 2 S 4 and β-Cu 2 HgJ 4 type structures with the same ordered arrangement of vacancies. In MnIn 2 Te 4 , however, the different cations are distributed randomly over the occupied tetrahedral sites.

Crystals of [Fe(NO) 2 PØ 3 Cl] are monoclinic with a = 1.6265(7) [nm], b = 1.4495(7) [nm], c = 1.5609(6) [nm] and β= 96.86(2) deg.; the space group is C 2/c. The structure was determined by three dimensional Patterson and Fourier methods on the basis of 2266 independent intensities. The unit cell consists of 8 isolated molecules. Within the coordination polyhedron, a distorted trigonal pyramid, the Cl, Fe, P plane approximately represents a mirror plane of the molecule. The nitrosyl ligands are bent towards each other with an N-Fe-N angle of 115.6(3) and Fe-N-O angles of 166.4(5) and 165.5(5) deg. The geometry of the molecule is discussed with regard to other dinitrosyl complexes and to electronic structure.

The crystal structure of α-Bromo(2-dibutylaminoethanolato)copper(II) has been determined by single-crystal X-ray diffractometer methods using 1488 independent reflexions and MoKα radiation. The compound crystallized in the orthorhombic space group P2 1 2 1 2 1 with four dimers in a unit cell of dimensions a = 21.235(13), b = 15.220(8) and c = 8.390(5) Å. The structure was refined by least-squares methods giving a final residue of R = 0.087. The dimer molecules with Cu-Cu-separations of 3.019(4) Å consist of nonplanar Cu 2 O 2 -rings with Cu-O-distances of 1.92(2) Å (mean value). The coordination around each copper atom is distorted square planar. The averaged Cu-N-distance is 2.06(2) Å and Cu-Br-separations are 2.333(4) A. In good agreement with the calculated density of 1.55 g cm -3 is the experimental value of 1.53(3) g cm -3 .

Methylindium-dichlorid kristallisiert in der tetragonalen Raumgruppe I4̅ mit den Gitterkonstanten a = b =13.628 Å und c = 6.333 Å. Die Elementarzelle enthält acht Formeleinheiten. Indium ist in starker Verzerrung trigonalbipyramidal von einem Kohlenstoffatom (der Methylgruppe) und vier Chloratomen (mit deutlich verschiedenen In–Cl-Abständen) umgeben.

The stable complex, [Pt(WS 4 ) 2 ] 2- , has been prepared as the tetraphenyl phosphonium salt by the reaction of K 2 [PtI 6 ], (NH 4 ) 2 WS 4 and (C 6 H 5 ) 4 PCl. Its vibrational and electronic spectra are reported. The [Pt(WS 4 ) 2 ] 2- ion has D 2 h symmetry with a planar PtS 4 chromophore. The vibrational frequencies have been assigned by a detailed analysis.

Pure alkaline earth halides MX 2 with M = Mg, Ca, Sr, Ba and X= Cl, Br, J were prepared by reaction of the metals with the corresponding ammonium halides in NH 3 as solvent. Brown Ca 2 PCl and dark-brown-violet Sr 2 PCl were obtained by reaction of metal chloride, metal and red phosphorous in the ratio 1:3:2. Analytical results, densities and lattice constants are given.

The reaction of trifluoromethylchlorosulfane with an excess of hydrogensulfide yields trifluoromethyldisulfane. The new compound has been characterised by its IR, Raman, 19 F and 1 H NMR, UV and mass spectrum, melting and boiling point and by vapour pressure data. The result of some chemical reactions are reported. Furthermore, previously unreported NMR and mass spectral data of CF 3 SH, CF 3 S 3 CF 3 and CF 3 S 4 CF 3 are given.

Single crystals of Cu 4 V 2.15 O 9,38 were prepared by hydrothermal synthesis. The composition was confirmed by analysis and crystal structure investigation. Cu 4 V 2.15 O 9,38 has an orthorhombic unit cell : a = 15.021, b = 8.564 and c = 6.055 Å, space group D 2 4 P 2 1 2 1 2 1 . The structure consists of a network made up of chains of edge-shared Cu-O 6 octahedra. The chains are linked by Cu-O 6 octahedra building up a wave-like layer parallel to the b/c plane. The layers are linked to each other by V—O 4 tetrahedra and two sorts of trigonal bipyramids one of them containing copper. The center of the other one is statistically filled with vanadium.

MgAl 2 Te 4 , MgGa 2 Te 4 and MgIn 2 Te 4 were prepared by direct synthesis from the elements at 1000°C. MgIn 2 Te 4 crystallizes tetragonal in a variation of the zincblende structure. The vacancies are ordered as in β-Cu 2 HgJ 4 , the Mg- and In-atoms are distributed randomly in the cation sites of this structure.

In the direction of the crystallographic c-axis MgPt(CN) 4 · 7 H 2 O has a relatively low Pt-Pt-distance (3.15 Å at 300°K). Thus the optical behaviour shows inter-molecular interactions. Single crystal polarized emission and absorption spectra were measured between 300°K and 5°K. In this temperature range the emission peaks shift to the red by about 1,100 cm -1 . This is attributed to a decrease in Pt-Pt-distance. MgPt(CN) 4 · 7 H 2 O undergoes phase transitions at about 166°K and 60°K. To interprete the solid state emission and absorption behaviour the Davydov theory is applied. The two lowest excited bands of electronic origin are assigned to the symmetries Γ 2u (κ) and Γ 5u (κ) in the double group D′ 8h ·

The phase diagram of the system As—Te has been determined. The density and the electrical conductivity of the melts were measured as a function of temperature and concentration. The density increases with increasing temperature. The electrical conductivity has a minimum near 40 mol% As. This minimum becomes less pronounced with increasing temperature. Both observations indicate, that polymeric units exist in these melts, which are destroyed at higher temperature.

The four 185 Re, 187 Re—NQR-transitions of RbReO 4 were measured. From the NQR-coupling constants, asymmetry-parameter and normal temperature-coefficient in the range of 77-300°K one can conclude, that the anomalons temperature dependence of the NQR-frequencies of NH 4 ReO 4 is not caused by the absolute values of certain lattice parameters. An experimental correlation of the Re—NQR-coupling constants of scheelite-structured perrhenates with the length of the elementar cell was found and discussed.

The 22 Si NMR spectra of the mixed halides of silicon, SiWXYZ, W, X, Y, Z = Cl, Br, J, have been recorded. The chemical shift of these compounds can be rationalized in terms of substituent effects. Relations to the isoelectronic aluminium and phosphorus compounds are discussed. The 99 Si spectra of the simple chloropolysilanes have been assigned. A complication arises from the fact that SiCl 3 - and SiCl 2 -groups give about the same values of the chemical shift.

The infrared spectra of four erbium β-diketonates have been recorded in KBr phase on Perkin -Elmer 521 grating spectrophotometer. About thirty bands in each case have been observed and assigned to different modes of vibration. Single ring analysis has been used in interpretation of the bands.

The infrared and Raman spectra of potassium and tetramethylammonium salts of the dinuclear anions M 2 OX 10 4- and M 2 NX 8 (H 2 O) 2 3- , with M=Ru, Re and X=Cl, Br, have been registered and assigned on the basis of a normal coordinate analysis. The totally symmetric vibrations ν s Μ 2 Ο (ν s M 2 N), ν s MX a,x (ν s M—OH 2 ) and δ s OMX (δ s NMX) show considerable mixing. The force constants of the bridge bonds are 3.9 mdyn/Å for the μ-oxo-and 5.1 mdyn/Å for the μ-nitrido-compounds, the respective stretch-stretch interaction constants 0.45 and 0.6 mdyn/Å.

The visible and near IR spectra of the ammonium salt of cupferron and manganese, cobalt, nickel and copper divalent cupferrate complexes are investigated. New absorption bands observed are given and assigned using the Tanabe-Sugano diagrams. In the absorption spectra of the divalent transition metal cupferrates a characteristic shift in the maxima and minima appears. Solvent effects on this shift were investigated.

The complexes Bis(η-cyclopentadienyl)-1,1-dithiolatovanadium(IV) [VCp 2 (S 2 C=Y)] (Y = S,NCN,C(CN) 2 ,C(CN) (CO 2 Et),C(CO 2 Et) 2 )* and Bis(η-cyclopentadienyl)-1,2-dicyanoethylene-1,2-dithiolatovanadium(IV) [VCp 2 (S 2 C 2 (CN) 2 )] are prepared by reaction of [VCp 2 Cl 2 ] and the appropiate alkali metal salt K 2 S 2 C=Y or Na 2 S 2 C 2 (CN) 2 . The complexes are characterized by molecular weight, electric conductivity and magnetic measurements. The IR, electronic and ESR spectra are discussed.

Poly-1-vinyl-2-pyrrolidinone with Mn 2 (CO) 10 , Fe(CO) 5 , Co 2 (CO) 8 and Ni(CO) 4 in methylene chloride forms the following complexes: [Mn(C 6 H 9 NO) 5 ] n , Fe(C 6 H 9 NO) 5 ] n , [[Co(C 6 H 9 NO) 5 ] [Co(CO) 4 ] 2 ] n and [Ni(C 6 H 9 NO) 4 ] n . The IR spectra are discussed.

The reaction of SbBr 3 with the complex metal carbonyl anions [π-C 5 H 6 (CO) 3 M]Na (M = Mo, W) leads to the formation of transition metal antimony bromides π-C 5 H 5 (CO) 3 M-Sb̅-Br 2 , which can be further metallated, yielding the stable species [XXX] All bromine substituted transition metal stibines prove to be excellent coordinating ligands and can easily be introduced into activated metal carbonyls. The interaction of π-C 5 H 5 (CO) 3 M-Sb̅Br 2 , with bromine results in a quantitative Sb-M bond cleavage, presumably via primary formation of pentavalent intermediates. All new compounds are fully characterized by means of IR, 1 H NMR and mass spectroscopy.

Transition metal derivatives of phenylphosphine, C 6 H 5 PH 2 ML with ML = Cr(CO) 5 , C 5 H 5 Mn(CO) 2 and CH 3 C 5 H 4 Mn(CO) 2 may be lithiated by lithium-n-butyl. The synthesis of CH 3 C 5 H 4 Mn(CO) 2 P(C 6 H 5 ) (H)Li and CH 3 C 5 H 4 Mn(CO) 2 P(C 6 H 5 )Li 2 as well as there reaction with D 2 O are described.

Considering certain kinds of pharmacologic activity previously found in semicarbazide derivatives of a number of compounds we decided to synthesize molecules containing a semicarbazide or thiosemicarbazide moiety for subsequent pharmacological testing. For a start we combined the semicarbazide grouping with another potentially active component, the 4-hydroxycoumarin ring system.

The photochemical behaviour of α-, β- and γ-chlordene in solution was examined. UV-irradiation in methanol showed that direct excitation leads to [2 π + 2 π]-photocycloaddition and photodechlorination reactions. The proposed structures of the photoproducts are supported by spectroscopic data (MS, IR, PMR). The insecticidal properties of several products of photoisomerisation and photodechlorination reactions were measured and compared with those of the original compounds.

The adducts from carboxylicacid chlorides and -anhydrides of aromatic Schiff-Bases differ fundamentally in their spectroscopic behavior compared with the hydrochlorides. A real addition on the azomethine double-bond is shown by 1 H NMR, 13 C NMR and UV spectroscopy.

A novel route to octahydroacridine-1,8-diones, starting from cyclohexane-1,3-dionemonoimines and triethylorthoformate is described. The method is superior to former ones. The obtained octahydroacridines can be transformed into several derivatives.

The quantum efficiency of the formation of (arene)Cr(CO) 2 (pyridine) (arene=benzene, mesitylene) is reported as a function of the irradiation wavelength of (arene)Cr(CO) 3 and as a function of pyridine concentration. The quantum efficiency is independent of pyridine concentration in the range 0.008-0.17 M. The quantum efficiency is 0.72 ± 0.07 upon 313, 366, or 436 nm irradiation. The (arene)Cr(CO) 3 complexes are found to quench triplet excited benzil at a diffusion controlled rate and the quenching is accompanied by reaction of the (arene)Cr(CO) 3 . The reaction product which presumably arises from CO release is the same as that obtained from direct irradiation of (arene)Cr(CO) 3 in the presence of benzil. However, the triplet sensitized reaction occurs with a quantum efficiency of only 0.15 ± 0.05 in contrast to the high substitution efficiency (0.72 ± 0.07) of (arene)Cr(CO) 3 upon direct irradiation.

The mass-spectrometric investigation of esters and thiolesters of benzoic, thiobenzoic, salicylic and thiosalicylic esters shows that an analytical distinction with aid of the ortho effect is only possible under certain conditions between 1,2-disubstituted aromatic compounds and the other constitutional isomers. Absent or small intensive signals of rearrangement-ions do not exclude such a constitution. The apparent anomalous behaviour of the S-methyl, S-tolyl and O-tolyl esters is rationalized by energy considerations. The influence of the enthalpy of formation of the neutral particles on the product distribution (α-cleavage/ortho effect) is discussed.

The number of linear independent dissociation equilibria of spectrophotometric titration may be determined experimentally by means of absorbance diagrams and absorbance-difference-quotient diagrams. The different types of spectrophotometric titration curves in two-step titrations are classified. By simulation of systematic error functions the limits of pK determination using turning points of two-step titration curves are demonstrated. By means of certain absorbance diagrams it is possible to determine the absorbance of pure ampholyte and to construct the absorbance triangle of all three pure components. From this triangle all concentration- vs pH-curves and the pK-values of a bivalent protolyte may be established. To avoid electrometric pH-measurements new methods are devised to calculate the difference of pK-values of bivalent protolytes. These new methods are demonstrated using as examples o-phthalic acid, 3-hydroxy-4-nitrobenzoic acid and sozoiodolic acid.

Single crystals of SrPbO 3 could be prepared by oxygen-high-pressure-synthesis (PO 2 > 3500 at, t = 450°C). Single crystal X-ray diffraction data confirm the space group D 2h 16 -Pnma. SrPbO 3 belongs to the orthorhombic distorted Perowskit type with a = 5.964, b = 8.320, c = 5.860 Å. The atomic positions were refined.

By reaction of silver-3,5-difluoro-1,1,3,5-tetraoxo-1,3,5,2,4,6-trithiatriazene(1,3,5-S VI ) with alkyljodids a new inorganic ring-system is formed, containing two sulfanuric-fluoridegroups and one alkylsulphimide-group. The structures are proofed by NMR and other structure-isomeres can be excluded.

The infrared and Raman spectra of the perovskites SrLaMgSbO 6 and Ba 4 LiSb 3 O 12 are reported and discussed in terms of antimonate internal modes.

Linear relationships have been established between SS bond distances and both SS force constants and SS stretching frequencies. Bond distances are derived for S 2 – , S 3 – , and S 4 2+.

The new compound hexa(isothiocyanato)-disilane, Si 2 (NCO) 6 , is prepared by reaction of Si 2 Br e and AgNCO in toluene, and is characterized by mass, vibrational as well as UV spectra.

Pyridine-2-thiolato complexes of copper(I) and cobalt (III) have been prepared from copper(II)- and cobalt(III)-acetylacetonate with pyridine-2-thiol as well as by reacting CuCl(pyridine-2-thiol) 3 and CoCl 2 -(pyridine-2-thiol) 2 with a base. The copper(I) complex forms an addition product of low stability with triphenylphosphine. The cobalt complex is monomeric whereas according to its mass spectrum pyridine-2-thiolato-copper(I) appears to be tetrameric.

The 35 Cl NQR spectrum od dimethylcarbamoylchloride-trichloroborane shows an extraordinarily high shift of the C—Cl resonance compared to the uncomplexed dimethyl-carbamoylchloride. The reasons are discussed.

The methyl group of the acetyl groups in 2,4-diacetyldeuterohemin-OMe has been selectively deuterated. After removal of the iron, D 6 -2,4-diacetyl-deuteroporphyrin-OMe can be reduced to the corresponding hematoporphyrin and subsequent dehydration gives deuterated vinylic groups for protoporphyrin IX–OMe.

Cyclooctatetraene dimerises at high pressure (12 Kbar, 20°C) to the isomers 2 and 3. At 120°C compound 2 isomerises quantitatively to compound 3. The conversion rate of Hexamethyldewarbenzene to Hexamethylbenzene at high pressures depends on kind of solvent, whereas the influence of temperature is small in the range between 20° and 80°C.

The photoreaction of [(η-phenyl)phenylethylphosphane] (η -2,3-dimethylbutadiene)-iron(0) with 2,3-dimethylbutadiene results in replacement of the arene ligand by the diene, leading to a bis(diene)phosphane iron(0) complex.

Reaction of dialkyl monothionooxalate with ortho-phenylenediamine yields 3-alkoxy-2-oxo-quinoxaline, whereas benzothiazole-2-carboxylic acid ethyl ester 8 is obtained from o-aminothiophenole.