Band 31, Heft 9

The title compound, which may be prepared from C 5 H 5 (CO) 2 Mn—P(Ph)Cl 2 and Fe 2 (CO) 9 crystallizes in the monoclinic space group C 2/c with a = 1579(2), b = 1592(2), c = 1790(3) pm, β = 97.2(1)°, Z = 8. The structure was solved by direct methods. Full matrix refinement led to R 1 = 0.066. The compound contains a threemembered metallocycle with two iron and one manganes atoms. Each iron atom bears three terminal carbonyl groups; the two CO-ligands of the C 5 H 5 Mn(CO) 2 fragment form unsymmetrical bridges with the two iron atoms. The metal triangel is capped by a Ph—P group with a triply bridging phosphorus atom.

The title compound 1 contains complex stabilized 1,2-diphenyldiphosphane. It crystallizes in space group P2 1 /c with a = 1095(1), b = 1145(1), c = 1186(1) pm, β= 124.73(5)°, Z = 2. The structure has been solved by coventional methods; full matrix refinement converged at R 1 = 0.045. 1 shows crystallographic inversion symmetry and thus contains a meso-1,2-diphenyldiphosphane ligand. The P–P-distance is 225.8 pm, the Mn–P bonds are rather short (221.6 pm).

Silver-N-cyclohexylamidoperchlorate crystallizes in the monoclinic space group P2 1 /n with the cell parameters a = 12.810 A, b= 24.710 Å, c= 6.051 Å, β= 90.0°. The crystal structure is built up by —N—Ag—N—Ag-chains. The N—Cl distance is much longer than in K 2 NClO 3 , but slightly shorter than in other compounds with N—Cl bonds.

A new compound having the same composition as zircon, ZrSiO 4 , but differing from it in its structure has been obtained by heating zircon particles to a temperature of 5000 to 10000°K. According to X-ray powder diffraction data the structure and within limits of error also the unit-cell dimensions are identical with that of monoclinic baddeleyite, ZrO 2 . This suggests that the baddeleyite lattice can not only accommodate 10 molecular % SiO 2 as is already known for some time, but substantially more, unless it is assumed that some kind of submicroscopic exsolution of amorphous SiO 2 has taken place.

Cubic γ-Na 2 PtO 3 (α = 4.487 Å), Na 4 PtO 4 (α = 4.52 Â) and tetragonal Na 8 PtO 6 (α = 7.965, c = 4.053 Å) were prepared by thermal reaction of sodium oxide or peroxide with platinum powder. Similar as for α,β-Na 2 PtO 3 and Na 2 PtO 2 the crystal structures of the new compounds can be related to the sodium chloride structure with a partial ordered superstructure in Na 8 PtO 6 or without long range ordering in γ-Na 2 PtO 3 and Na 4 PtO 4 .

Sr 2 Cu 3 O 4 Br 2 was prepared and examined by single crystal X-ray work. It is isotypic with Sr 2 Cu 3 O 4 Cl 2 ; space group D 4h 17 - I4/mmm with a = 548.9 and c = 1330.6 pm. A discussion of the result in respect of the octahedral distortion is given.

Tetramethylarsonium-, as well as tetramethylstibonium-monomethyltrichloroindate crystallizes in the monoclinic space-group Pc with two formula units in the cell. In both structures we found isolated (CH 3 )4M + - and (CH 3 )InCl 3 - - tetrahedra (M = As, Sb), from which the anionic one in markedly distorted. The distances between these isolated tetrahedral cations and anions are not equal. The tetrahedrical cations and anions form double-layers.

Sodium bis(L-aspartato)chromate(III), a complex with L-aspartic acid as tridentate ligand, has been prepared by reaction of chromium(III)chloride, L-aspartic acid and sodium hydroxid. Infrared, electronic absorption and circular dichroism spectra of three isolated isomers have been measured.

Adducts of macrocyclic polyethers (crown ethers) and aminopolyethers 1,2 having hydrogen bonds with polar organic molecules, especially with CH-acidic compounds, are described. These can be isolated as solids, and are, as a rule, stoichiometrically consistent. The chemical shift of the 1 H NMR signals of the adducts of malononitrile with various crown ethers corresponds to the anionic reactivity of potassium complexes of the crown ethers in the course of nucleophilic substitution reactions.

The exchange of H versus D between [HAlNC(CH 3 ) 3 ] 4 and [DAlNC(CH 3 ) 3 ]4 leads to an equilibrium mixture of H 4-n D n [AlNC(CH 3 ) 3 ]4 with statistical distribution of H and D. This is, as expected, not the case for the H/Cl-distribution achieved between [HAlNC(CH 3 ) 3 ] 4 and [ClAlNCH(CH 3 ) 2 ] 4 . Although a series H 6-n Cl n [AlNCH(CH 3 ) 2 ]6 can be detected besides H 4-n Cl n [AlNCH(CH 3 ) 2 ]4 and H 4-n Cl n [AlNC(CH 3 ) 3 ] 4 the absence of alkyl group exchange proves that the redistribution of Al-substituents occurs without transfer of XAlNR units by an exopolyhedral exchange mechanism involving pentacoordinate aluminium.

Besides the mica-type layer silicates, uranium micas (Me{UO 2 PO 4 }) are excellent examples of layer compounds which incorporate long chain alkyl compounds between the layers with formation of bimolecular films. They are recommended as models for the study of phase transformations of bimolecular films. Comparison between layer silicates and uranium micas reveals the matrix effect of the inorganic sheets. Bimolecular films between silicate sheets rearrange into well organized kink blocks by two-dimensional cooperative reactions. In uranium micas the different lateral symmetry but identical packing density makes kink block formation less regular and proceeding only by one-dimensional cooperative reactions.

The reaction of triisopropyl- or tricyclohexylhalosilanes with silver salts gives the corresponding silyl nitrites and silyl nitrates. The insertion reaction of sulfur trioxide or dichlorocarbene into the silicon hydrogen bond of triisopropylsilane and tricyclohexylsilane yields the sulfates and the dichloromethyl derivatives, respectively.

Reaction of (NPCl 2 ) 2 NSOCl or (NPCl 2 ) 2 NSOF with benzene in the presence of AlCl 3 yields (NPCl 2 ) 2 NSOPh. By the same procedure two isomeric forms of NPCl 2 (NSOPh) 2 can be obtained from cis-NPCl 2 (NSOCl) 2 . The phenylated products were characterized by IR, mass and 31 P NMR spectra. Reactions of one of the isomers of NPCl 2 (NSOPh) 2 with (CH 3 ) 2 NH yield NPClN(CH 3 ) 2 (NSOPh) 2 (molar ratio 1:2) and NP[N(CH 3 ) 2 ] 2 (NSOPh) 2 (molar ratio 1:6.8). The structures of the amino substituted derivatives were determined by means of 1 H NMR measurements.

The alkali metals Rb and Cs and their suboxides Cs 11 O 3 , Cs 7 O (≙ [Cs 11 O 3 ]Cs 10 ) and [Cs 11 O 3 ]Rb 7 have been investigated by UPS (HeI). Extremely narrow O2p levels are observed, as well as significant differences in the binding energies of the 5p levels of chemically different Cs-atoms. From energy loss structures (surface plasmons) electron concentrations are determined. The results are discussed in terms of structurally derived bonding models. The alkali metal suboxides are of importance in IR-sensitive Ag/Cs/O-photocathodes.

Polarized absorption spectra of the ions Mo(CN) 8 4- and W(CN) 8 4- were measured on single crystals of the compounds K 4 Mo(CN) 8 · 2 H 2 O and K 4 W(CN) 8 · 2 H 2 O over the spectral region 10-47 kK and at temperatures from 300°K to 4.2°K. The results obtained were interpreted on the basis of the ligand field theory. According to their d → d-spectrum, these complex ions in the crystalline state have a quasi-dodecahedral coordination structure with the exact symmetry D 2 . The deviation from the ideal dodecahedral structure is appreciably smaller at low temperatures than at room temperature. Contrary to the results of earlier X-ray structure determinations, the only space group which can be assigned to the crystals of K 4 Mo(CN) 8 · 2 H 2 O and K 4 W(CN) 8 · 2 H 2 O is C 9 2v .

Tricarbonyl-η-1,3,5-cycloheptatriene-chromium(0) (1) reacts photochemically with trimethyl-phosphine, -arsine, or -phosphite respectively to form the complexes CrC 7 H 8 (CO) 2 L (2-4) (L = P(CH 3 ) 3 , As(CH 3 ) 3 , P(OCH 3 ) 3 ) and CrC 7 H 8 (CO)[P(OCH 3 ) 3 ] 2 (5) The 1 H, 13 C and 31 P NMR spectra of these complexes are temperature dependent as a result of a hindered motion of the C 7 H 8 ligand. By this motion the dissimilar stereoisomers of the complexes, which are present, partly in very different concentrations, are interconverted. The energy barriers of the isomerisations were determined.

The electronic absorption spectra, absolute fluorescence spectra and fluorescence quantum yields as well as the fluorescence decay times of nine 1,3-diphenyl-2-pyrazolines substituted in the para-position of the 1-phenyl ring and of 19 substituted in the paraposition of the 3-phenyl ring were measured in degassed benzene at room temperature. The fluorescence quantum yields are about 0.90 with the exception of the NO 2- and J-substituted 1,3-diphenyl-2-pyrazolines. The fluorescence decay time ranges from 2 to 4 nsec. The natural fluorescence lifetimes determined experimentally agree well with those calculated from the absorption spectra according to STRICKLER and BERG. A plot of the Hammett σ p -values versus the energies of the absolute fluorescence maxima of the psubstituted 1- and 3-phenyl ring of the 2-pyrazoline system shows a statistically significant linear correlation with moderate precision. The linearity between ground state substituent constants and fluorescence energies reveals that the relative importance of the inductive and the resonance effects of the substituents remains constant during the transition from the ground state to the relaxed excited singlet state. In the excited singlet state of 1,3-diphenyl-2-pyrazoline the p-substituents provide more room for a larger charge displacement in the intramolecular charge-transfer. The structural bands in the fluorescence spectra resulting from strong electron accepting substituents in the para-position of the 1-phenyl ring are considered as the result of the ring breathing vibration due to a local excitation of the 1-phenyl ring.

Insect sex attractants are of considerable practical interest inasmuch as it is possible with their aid to control and to combat certain damaging species of insects selectively with minimum damage of the environment. Instead of the known multistage syntheses the metathesis reaction offers the possibility to produce some insect sex pheromones inexpensively on a large commercial scale starting with cheap petrochemicals. Thus, the sex attractants of the common housefly, of the face fly and of the gypsy moth could be prepared by using suitable starting alkenes and homogeneous or heterogeneous catalysts.

Mono-, di- and trinitroxylradicals are investigated in solution by ESR spectroscopy. The ESR spectra of all multispin systems studied can be interpreted under the assumption of an exchange interaction of the radical electrons. The exchange energies J are evaluated by comparison of experimental and theoretical line positions. The temperature dependence of J leads to activation energies around 1.5 Kcal/Mol. The analysis of proton hfs of the biradicals indicates the existence of two radical species which slow and fast exchange rates.

5,6-Didehydro-11,12-dihydro-dibenzo[a,e]cyclooctene is a highly strained cycloalkyne. At room temperature it exists in a chiral C 2 -conformation. A direct proof is the AA′ BB′ pattern of the 1 H NMR spectrum, for which also a computer calculation was performed. The spectroscopic fingerprints of the ring strain and the ring inversion are discussed.

The γ-radiolysis of N-acetyl-glucosamine in deoxygenated (N 2 O saturated) and oxygenated (N 2 O/O 2 saturated) solutions has been investigated. Eleven products have been characterised and their G-values estimated. Deoxygenated conditions: The principal products identified are 1-acetamido-1,3-dideoxy-2-pentulose (4), 1-acetamido-1-deoxy-2-pentulose (5), 2-acetamido-2,3-dideoxyhexos-4-ulose (6), 2-acetamido-2-deoxy-hexodialdose (7), 2-acetamido-2-deoxy-hexos-5-ulose (8) and 2-acetamido-2-deoxy-gluconic acid (9). Products 1 to 3 contain 3-5 carbon atoms (acetamido group eliminated). Their yields are low. Oxygenated conditions: G values of 5, 7, 8 and 9 are increased, whereas compounds containing a deoxy-keto group (4 and 6) are absent. C-C-bond scission is more important in the presence of oxygen. 2-Acetamido-2-deoxy-tetrodialdose (10) has been identified and a number of products with 5 carbon atoms in the chain retaining the acetamido group (11) have been recognised. Mechanisms for the formation of products are proposed.

The reaction between isopropylamine and isopropylammonium hexachloroantimonate(V) yields a red product of the composition C 12 H 40 Cl 8 N 4 Sb. The X-ray structure analysis showed that this is a mixed valence compound of SbCl 6 3- and SbCl 6 - octahedra.

Tetraphenylphosphonium tetrathiorhenate(VII) is shown to be isostructural with tetraphenylarsonium tetrachloroferrate(III) and by means of radial distribution analysis the average metal ligand distance was estimated as d(ReS) = 2.155(30) Å.

Mössbauer data of low spin Fe 2+ -ions in nitro complexes A I 2 PbFe(NO 2 ) 6 [A I : K, Tl, Rb, Cs] are presented. Explicitly the dependence of the isomer shift δ on the FeN bond length is studied and correlated with the ligand field parameters Δ of the corresponding Ni 2+ - and Cu 2+ -compounds.

The vibrational frequency of Al 35 Cl in solid neon and argon has been measured to be 470 cm -1 and 455 cm -1 . The 35 Cl/ 37 Cl isotopic splitting is 5.4 ± 0.2 cm -1 in argon matrix. The IR absorption of AlBr has been recorded in neon, argon and nitrogen matrices (370, 357, 349 cm -1 ). In solid argon the frequency shift due to 81 Br/ 79 Br isotopes could be resolved (0.95 ± 0.2 cm -1 ). The fundamental v 3 of monomeric AlBr 3 is observed at 508.4 cm -1 in an argon matrix.

The preparation of the first chlorodiorganylthioarsorane is reported. Amidodi(tertbutyl)arsine and sulfur react to give amidodi(tert-butyl)thioarsorane, which is converted into chlorodi(tert-butyl)thioarsorane by a solution of HCl in ether. Some reactions of chlorodi(tert-butyl)thioarsorane are described.

The title compound was synthesised and its structure determined by X-ray crystallography. The structure contains a hydrogen bond between the OH group of the alcohol and the phosphoryl oxygen atom. The P–N bond lengths are significantly different and the differences can be attributed to varying ρπ—dπ interactions along the bonds.

A new and convenient synthesis of thieno-(2,3-b)quinoline starting from methyl-3-vinylquinolin-2(1H)-one-4-carboxylate is described.

In contrast to the corresponding butyl ions the [M–CH 3 ] + ions from isomeric pentylbenzenes do not isomerise completely to a mixture of interconverting structures prior to decomposition.

Electrical conductivity of thioxanthene single crystals has been observed. The electrons, injected from the electrodes or freed by sulphur atoms, are responsible for the electrical properties. The activation energy for the conduction is higher than in thianthrene, it depends maybe on the number of S atoms in the molecule.

The synthesis of 15-acetoxydihydrocatharanthine, of key intermediate in the synthesis of the anti-cancer alkaloid vinrosidine (3), is described by a novel modification of the PREVOST reaction.