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61	Author	Gemot Frenking, Jochen Schmidt, Helmut Schwarz	Requires cookie*
	Title	Quantenmechanische Berechnungen zu pseudo-einstufigen (C-C)-Spaltungen bei Radikalkationen von Carbonsäuren Quantum Mechanical Calculations on Pseudo-One-Step Cleavages of Carbonic Acid Cation Radicals
	Abstract	Extensive quantum mechanical calculations on the unrestricted MINDO/3 level reveal that for some ionised carbonic acids the energetically most feasible pathway for uni-molecular C-C cleavage cannot be described as being a one-step process. In complete agreement with experimental results the computational data are consistent with an inter-pretation of the reaction as being a two-step process, in which the reaction commences with a hydrogen migration from a CH-bond onto the ionised C = 0 group. The dissociation is completed with a radical induced C-C cleavage thus generating quite stable protonated unsaturated carbonic acids. Whereas the MINDO/3 results clearly show that the two-step process is energetically favoured over the direct C-C cleavage, this computational method fails badly in explaining the experimentally established fact that in the two-step sequence the hydrogen migration is the rate-determining step. This failure is due to the MINDO/3 inherent weakness of overestimating the stability of cyclic ions, e.g. cyclic transition states as they are formed in the course of the hydrogen migration step. Single point ab initio calculations carried out on the 4-31G level substantiate this interpretation in that the transition state for the hydrogen migration is calculated to lie substantially higher than that for the actual C-C dissociation step, but is still much lower than that calculated for a direct simple bond cleavage process of the respective cation radical.
	Reference	Z. Naturforsch. 37b, 355—360 (1982); eingegangen am 23. Oktober 1981
	Published	1982
	Keywords	Potential Energy Surfaces, Carbonic Acids, Hydrogen Rearrangement, C-C Cleavage, Mass Spectrometry
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	Identifier	ZNB-1982-37b-0355
	Volume	37

62	Author	Klaus Burger, Friedrich Hein, Joachim Firl	Requires cookie*
	Title	Vom "criss-cross"-Schema abweichende Cycloadditionsreaktionen an das Azin-System [1] Zum Cycloadditionsverhalten von Hexafluoracetonazin gegenüber N.N-Dialkyl-cyanamiden [2] Cycloaddition Reactions of Azines Violating the "criss-cross" Cycloaddition Scheme [1] Cycloaddition Behaviour of Hexafluoroacetone Azine towards N,N-Dialkyl-cyanamides [2]
	Abstract	Cycloaddition Reactions, Trifluoromethyl Substituted Heterocyclic Systems, Long Range Coupling 9 JFF Depending upon the molar ratio of the educts and the reaction conditions used, hexa-fluoroacetone azine (1) reacts with N,N-dialkyl-cyanamides (2) to give 3,4,6-triazaocta-2,4,6-trienes (6) and/or 4,4-bis(trifluoromethyl)-l,4-dihydro-l,3,5-triazines (7). Cyclo-addition reactions of 6 with teri-butyl isocyanide and l-diethylamino(propine) are de-scribed. IR, *H, 19 F, and 13 C NMR data of the new compounds are discussed.
	Reference	Z. Naturforsch. 37b, 361—367 (1982); eingegangen am 11. August 1981
	Published	1982
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	Identifier	ZNB-1982-37b-0361
	Volume	37

63	Author	R. K. Broszkiewicz+, T. Söylemez, D. Schulte-Frohlinde	Requires cookie*
	Title	Reactions of OH Radicals with Acetylacetone in Aqueous Solution. A Pulse Radiolysis and Electron Spin Resonance Study
	Abstract	Pulse radiolysis experiments monitoring optical absorbance as well as conductivity and in-situ ESR radiolysis studies show that the OH radical reacts with the enol (k = 8.6 x 10 9 M _1 s _1) and the enolate (k = 7.4 X 10 9 M _1 s -1) forms of acetylacetone by addition to the C = C double bond in aqueous N2O saturated solution. The OH reaction with enol leads to equal amounts of two radicals, CH3COCHOHCOHCH3 (2) and CH3COCHC(OH)2CH3 (4), as determined by scavenger reactions. At pH less than 1 the radical CH3COCHCOCH3 (1) is observed by ESR spectroscopy showing that radical 2 and/or 4 eliminate water by proton catalyzed reactions. Under alkaline condition the OH adducts to the enolate eliminate OH -with rate constants larger than 10 5 s -1 leading to radical 1. G(OH") is determined to be 5.6 showing that addition is the main reaction of OH with enolate. To a much smaller degree the OH radical is proposed to abstract an H atom from that CH3 group which is attached to the C —C double bond in enol and enolate, producing substituted allyl radicals which absorb in the visible region. The reaction of OH with the keto form has not been observed indicating that the rate constant of this reaction is significantly smaller than those with enol and enolate.
	Reference	Z. Naturforsch. 37b, 368—375 (1982); received August 19 1981
	Published	1982
	Keywords	Pulse Radiolysis, OH Radicals, Acetylacetone, Reaction Mechanisms
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	Identifier	ZNB-1982-37b-0368
	Volume	37

64	Author	Peter Seidel, Ivar Ugi	Requires cookie*
	Title	Die Photoaddition von Bromtrichlormethan an Allyl-Systeme Photoaddition of Bromotrichloromethane to Allylic Systems
	Abstract	Photoaddition of Bromotrichloromethane, 1-Substituted 4,4,4-Trichloro-2-bromobutanes The preparation of various 1-substituted 4,4,4-Trichloro-2-bromo-butanes by photo-addition of bromotrichloromethane to allylic systems is described. Generally a more uniform product and a higher yield are obtained by this photoaddition than by the corresponding chemically initiated radical chain reaction.
	Reference	Z. Naturforsch. 37b, 376—379 (1982); eingegangen am 23. Oktober 1981
	Published	1982
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	Identifier	ZNB-1982-37b-0376
	Volume	37

65	Author	G. N. Schrauzer, LauraA. Hughes, Norman Strampach	Requires cookie*
	Title	The Chemical Evolution of a Nitrogenase Model, 20 Alkyl Molybdates(VI) and the Mechanism of Hydrocarbon Production by Nitrogenase [1]
	Abstract	Nitrogenase Model, Alkyl Molybdates Colorless alkylmolybdates(VI) of composition R-M0O3-are generated in aqueous solutions by the alkaline hydrolysis of complexes R-Mo(Bpy)(0)aBr (Bpy = 2,2'-bipyridyl, R = CH3 and higher alkyl). At room temperature in alkaline aqueous solution, the new organometallic derivatives of oxomolybdate(VI) are remarkably resistant against Mo-C bond hydrolysis. Decomposition occurs more rapidly on heating, affording unrearranged alkanes according to the eq.: R-M0O3-+ OH -RH + Mo04=. In acidic solutions, the methylmolybdate(VI) species decomposes with the formation of a mixture of methane and ethane while higher alkylmolybdates carrying hydrogen in the /^-position relative to molybdenum undergo Mo-C bond heterolysis by way of ^-elimina-tion: R-CH2CH2-M0O3--* • Mo +4 (aq) + H+ + R-CH = CH2. The Mo-C bond of alkylmolybdates is resistant to oxidants but is very sensitive to cleavage under reducing conditions. Reductive Mo-C bond cleavage occurs particularly rapidly in the presence of thiols and reduced ferredoxin model compounds. The latter reactions simulate the terminal steps of hydrocarbon producing reactions of nitrogenase with alternate substrates such as CN -, R-CN or R-NC, confirming previous mechanistic conclusions concerning the mechanism of nitrogenase action.
	Reference	Z. Naturforsch. 37b, 380—385 (1982); received September 1 1981
	Published	1982
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	Identifier	ZNB-1982-37b-0380
	Volume	37

66	Author	G. J. Bukovits, H. Budzikiewicz	Requires cookie*
	Title	Does a quasi-Thermal retro-Diels-Alder Decomposition Exist in Mass Spectrometry ? [1]
	Abstract	retro-Diels-Alder Decomposition, Mass Spectra, 5 ^-Steroids Evidence is produced to the effect that in mass spectrometry a quasi-thermal retro-Diels-Alder decomposition does not occur. This reaction has to be triggered by the positive charge in the molecule.
	Reference	Z. Naturforsch. 37b, 386—389 (1982); received September 7 1981
	Published	1982
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	Identifier	ZNB-1982-37b-0386
	Volume	37

67	Author	M. Schulte-Kellinghaus, V. Krämer	Requires cookie*
	Title	Preparation and Crystal Data of the Isotypic Aluminium (Gallium) Indium Sulphides AI2I114S9 and Ga2ln4S9
	Abstract	The title compounds were prepared by chemi-cal vapour transport. They crystallize in the space group P 3m 1 with the lattice parameters a = 7.532(3) (7.589(5)) and c = 36.54(2) (36.70(5))!. X-ray powder diffraction data are listed and the T,x phase diagram of the system AlInS3-In2S3 is shown.
	Reference	Z. Naturforsch. 37b, 390—391 (1982); eingegangen am 28. Oktober 1981
	Published	1982
	Keywords	Aluminium Indium Sulphide, Gallium Indium Sulphide, Crystal Data
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	Identifier	ZNB-1982-37b-0390_n
	Volume	37

68	Author	WilhelmF. Maier, Irina Thies, Paul Von, Ragué Schleyer	Requires cookie*
	Title	Heterogeneous Catalysis, VI Direct Reduction of Alcohols to Hydro- carbons [1]
	Abstract	Secondary and tertiary alcohols are converted cleanly to the parent hydrocarbons in the gas phase with H2 in the presence of a Ni/Al203 catalyst at 190 °C. Primary alcohols are de-hydroxymethylated; e.g., 1-hydroxymethylada-mantane (4) gives adamantane (1). Alumina alone, in the absence of Ni, results in the forma-tion of homoadamantane (5) from 4.
	Reference	Z. Naturforsch. 37b, 392—394 (1982); received August 13 1981
	Published	1982
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	Identifier	ZNB-1982-37b-0392
	Volume	37

69	Author	HansJoachim Breunig, Tevfik Severengiz	Requires cookie*
	Title	Reduktion von Butyl-und Phenylantimon(III)bromiden sowie von t-Butylantimon(III)chloriden mit Magnesium in Gegenwart von Trimethylchlorsilan: Konkurrenz von Sb-Sb-und Sb-Si-Verknüpfung Reduction of Butyl-and Phenylantimony(III) Bromides and of £-Butylantimony(III) Chlorides with Magnesium in the Presence of Trimethylchlorosilane: Competition of Sb-Sb and Sb-Si Coupling
	Abstract	Diphenyl(trimethylsilyl(stibine, Phenylbis(trimethylsilyl)stibine, Di-£er^butyl(trimethylsilyl)stibine, <er<-Butyl-bia(trimethylsilyl)stibine Butylantimony(III) bromides react with Mg in tetrahydrofuran (THF) even in presence of Me3SiCl exclusively with Sb-Sb-coupling: Starting from Bu2SbBr, Bu2SbSbBu2 is formed and BuSbBr2 is reduced to (BuSb)^. Sb-Si-coupling dominates in the reactions of PhaSbBr or -Bu2SbCl with Mg/Me3SiCl/THF yielding Ph2SbSiMe3 or <-Bu2SbSiMe3. Both Sb-Sb-and Sb-Si-coupling reactions are observed, when PhSbBr2 reacts with Mg and Me3SiCl yielding PhSb(SiMe 3)2 and (PhSb)x. The same reactants can also form the distibanes Ph2(SiMe3)2Sb2 and Ph(SiMe3)3Sb2. The reaction of -BuSbCl2 with Mg/Me3SiCl yields the stibines f-BuSb(SiMe 3)2 and Sb(SiMe3)3 together with (f-BuSb)i. In the reactions of«-BuSbCl2 or PhSbBr2 the ratio of Sb-Sb-and Sb-Si-coupling can be strongly influenced by using different reaction conditions.
	Reference	Z. Naturforsch. 37b, 395—400 (1982); eingegangen am 11. Dezember 1981
	Published	1982
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	Identifier	ZNB-1982-37b-0395
	Volume	37

70	Author	Cornelia Lensch, Oskar Glemser	Requires cookie*
	Title	Darstellung und Reaktionen von S.N-Bi8(heptafluorisopropyl)schwefelfluoridimid Preparation and Reactions of S,N-Bis(heptafluoroisopropyl)sulphurfluoride Imide
	Reference	Z. Naturforsch. 37b, 401—403 (1982); eingegangen am 8. Dezember 1981
	Published	1982
	Keywords	Sulphur-amide, N-hexafluoroisopropyl, S -[2 -chlorine-1, 1, 1, 3, 3, 3 -hexafluoro]isopropyl, Sulphurfluoride-imide, N-heptafluoroisopropyl, S-[2-chlorine-l, l, l, 3, 3, 3-hexafluoro]isopropyl, Sulphur-imide, N-heptafluoroisopropyl, S-dimethoxy
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	Identifier	ZNB-1982-37b-0401
	Volume	37

71	Author	Henri Brunner, MonikaE. Dylla, GabrieleA M Hecht, Willigis Pieronczyk	Requires cookie*
	Title	Synthese von ß-Diphenylphosphin-carbonyl-Verbindungen durch Umsetzung von Brommethyl-earbonyl-Verbindungen mit Diphenyl(trimethylsilyl)phosphin Synthesis of /9-Diphenylphosphine-carbonyl Compounds by Reaction of Bromomethyl-carbonyl Compounds with Diphenyl(trimethylsilyl)phosphine
	Reference	Z. Naturforsch. 37b, 404—406 (1982); eingegangen am 13. November 1981
	Published	1982
	Keywords	/3-Keto-phosphines, Amino-phosphines, Imino-phosphines, Synthesis, NMR Spectra, Optical Activity
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	Identifier	ZNB-1982-37b-0404
	Volume	37

72	Author	Ekkehard Lindner, Michael Stein	Requires cookie*
	Title	Darstellung, Eigenschaften und Reaktivität von 2-, 3-und 4-Chloracyl(diphenyl)phosphanoxiden Preparation, Properties and Reactivity of 2-, 3-and 4-Chloroacyl(diphenyl)phosphane Oxides
	Reference	Z. Naturforsch. 37b, 407—411 (1982); eingegangen am 26. November 1981
	Published	1982
	Keywords	Chloroacyl(diphenyl)phosphanes, Diphosphorylated Alcohols, MS, IR Spectra, NMR Spectra
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	Identifier	ZNB-1982-37b-0407
	Volume	37

73	Author	Bernd Wrackmeyer	Requires cookie*
	Title	U B-und 18 C-NMR-Spektroskopie von riic7o-Hexaalkyl-2.3.4.5-tetracarbahexaboranen(6) n B and 13 C NMR Spectroscopy of 7iüZo-Hexaalkyl-2,3,4,5-tetracarbahexaboranes(6)
	Reference	Z. Naturforsch. 37b, 412—419 (1982); eingegangen am 26. Oktober 1981
	Published	1982
	Keywords	U B NMR Spectra, 13 C NMR Spectra, nido -Hexaalky 1 -2, 3, 4, 5-tetracarbahexaboranes( 6)
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	Identifier	ZNB-1982-37b-0412
	Volume	37

74	Author	Martin Pfisterer, Günter Nagorsen	Requires cookie*
	Title	Darstellung, Struktur und elektrische Eigenschaften der Phase CaCu4As2 Preparation, Crystal Structure and Electrical Conductivity of CaCu4As2
	Abstract	Investigations in the system Ca-Cu-As resulted in the discovery of CaCuiAs2. The phase crystallizes in a rhombohedral structure (Trigonal axes: a = 417.3(6) pm, c = 2262(3) pm, space group R~3m). The conductivity varies from 47 to 89 (i2cm) -1 having a minimum at 250 K.
	Reference	Z. Naturforsch. 37b, 420—422 (1982); eingegangen am 27. Oktober 1981
	Published	1982
	Keywords	Calcium, Copper, Arsenide, Ternary Compound
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	Identifier	ZNB-1982-37b-0420
	Volume	37

75	Author	William Clegg, Uwe Klingebiel, GeorgeM. Sheldrick	Requires cookie*
	Title	Cyclisierungsreaktionen lithiierter Fluorsilanole und Aminofluorsiloxane - Kreuzdimerisierung eines Silicenium-Ylids Cyclisation Reactions of Lithiated Fluorosilanols and Aminofluorosiloxanes - Cross-dimerisation of a Silicenium-Ylid
	Abstract	KOH reacts with bis(isopropyl-trimethylsilyl)-amino-difluorosilane to give the fluoro-silanol 1. An aminofluorosiloxane 2 is obtained in the reaction of [(Me3Si)2N]2SiF2 with KOH via a 1,3-silyl-group migration. The four-membered SiOSiN ring 5 can be prepared in several steps from 1. Six-membered SiO rings 8-10 are formed in the reaction of 1,3-fluorosilanols 6 and 7 with butyllithium. Lithiated 2 reacts with PCI3 to give a four-membered P2N2 ring 11, and with 2-methyl-2-propenal to give two isomeric (2 + 4) cycloadducts 12 and 13. The silicenium ylid formed initially by thermal elimation of LiF from lithiated 2 in PE/THF cross-dimerises to give a Si2N2 ring 14. If the reaction is carried out in n-heptane, the product after recrystallisation from acetone, 16, is an isomer of 14. The crystal structures of 14 and 16 have been determined.
	Reference	Z. Naturforsch. 37b, 423—431 (1982); eingegangen am 14. Dezember 1981
	Published	1982
	Keywords	Fluorosüanols, Aminofluorosiloxanes, Cyclisation, Cross-dimerisation, Crystal Structure
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	Identifier	ZNB-1982-37b-0423
	Volume	37

76	Author		Requires cookie*
	Title	{©-«OH
	Abstract	, 3 6 1 und 2 können formal auch als "Mischpolymere" aus Polythiazyl ((SN)Z) und Poly-p-phenylen ((CelLOz) bzw. Poly-p-phenylensulfid ((CÖHIS)) an-gesehen werden. Für diese Substanzen sowie für 3-7 bot sich als universeller und schonender Syn-theseweg [6] die auch in der niedermolekularen S-N-Chemie besonders erfolgreiche Umsetzung von S-Cl-Verbindungen mit N-silylierten Diaminen und Diiminen an (Gin. (l)-(9)). Sonderdruckanforderungen an Prof. Dr. O. J. Sche-rer. 0340-5087/82/0400-0432/$ 01.00/0
	Reference	Z. Naturforsch. 37b, 432 (1982)
	Published	1982
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	Identifier	ZNB-1982-37b-0432
	Volume	37

77	Author	K. Dietz, H. Endres, H. J. Keller, W. Moroni, D. Wehe	Requires cookie*
	Title	The Structure of 5,10-Dihydro-5,10-diethylphenaziniumyl (E2P+)-2,2'-(2,5-cyclohexadiene-l,4-diyIidene)-bispropanedinitrilate(TCNQ) and its Difference to the Phenazine Doped Species E2P-P-(TCNQ)2 (P = Phenazine)
	Abstract	Phenazine free E2P-TCNQ, C28H22N6, Mr = 442.53 is monoclinic, P2i/c, a = 10.875(3), b = 14.679(4), c = 14.526(2) A, ß = 90.90(2)°, V = 2321.9 A 3 , Z = 4, dc = 1.27 Mgm~ 3 , the compound doped with 50% phenazine, E2P-P-(TCNQ)2 C52H34Nj2, Mr = 826.93, is tri-clinic, PT, o = 7.739(3), 6= 15.899(6), c = 17.037(7) A, a = 83.44(3), ß = 88.34(3), y = 83.19(3)°, V = 2067.7 A, Z = 2, dc= 1.33 Mgm-3 . E2P-TCNQ was refined to R = 0.066 for 1880 reflections. It consists of planar TCNQ anions and bent E2P cations (dihedral angle 17.7° along the line N-N) arranged in regular mixed stacks along c. The structure of E2P-P-(TCNQ)2 could be solved principally, but did not refine well (R = 0.165 for 1206 reflections). Regular segregated stacks of the phenazine and the TCNQ moieties are formed, and along the cationic stack the E2P+ cations and the neutral phenazine molecules alternate.
	Reference	Z. Naturforsch. 37b, 437—442 (1982); received October 14 1981
	Published	1982
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	Identifier	ZNB-1982-37b-0437
	Volume	37

78	Author	R. Tacke, A. Bentlage, W. S. Sheldrick, L. Ernst, K. Stoepel	Requires cookie*
	Title	Sila-Pharmaka, 24. Mitt. [1] Sila-Analoga von Nifedipin-ähnlichen 4-Aryl-2.6-cümethyl-1.4-dihydropyridin- 3.5-dicarbonsäure-dialkylestern, II Sila-Drugs, 24 th Communication [1] Sila-Analogues of Nifedipine-Like Di alkyl 4-Aryl-2,6-dimethyl-l,4-dihydropyridine- 3,5-dicarboxylates, II
	Abstract	In the course of systematic studies on sila-substituted drugs the nifedipine-like 1.4-di-hydropyridine derivatives 4 a, 4 b and 4 c were prepared and investigated with respect to sila-substitution effects. By X-ray diffraction analyses 4 a, 4 b and 4 c were found to be isostructural. The C/Si-analogues exhibit similar spasmolytic activities (in vitro, guinea pig ileum), comparable with that of nifedipine. However, the compounds differ sub-stantially in their in vivo activity, as measured by the antihypertensive effect on the renal-hypertensive rat. The experimental results are discussed with respect to the carbon/silicon exchange.
	Reference	Z. Naturforsch. 37b, 443—450 (1982); eingegangen am 25. September 1981
	Published	1982
	Keywords	Sila-Analogues of Nifedipine Derivatives, X-ray, Pharmacological Activity, Structure-Activity Relationships
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	Identifier	ZNB-1982-37b-0443
	Volume	37

79	Author	Hans Moser, Grety Rihs, Hanspeter Sauter, Entwicklung Forschung, Pflanzenschutz	Requires cookie*
	Title	Der Einfluß yon Atropisomerie und chiralem Zentrum auf die biologische Aktivität des Metolachlor The Influence of Atropisomerism and Chiral Centre on the Biological Activity of Metolachlor
	Abstract	The four stereoisomers of the grass herbicide Metolachlor, the isomerism of which is based on a combination of a chiral centre and a chiral axis, were prepared, and their absolute configurations determined by X-ray analysis. The synthesis was achieved by using optically active starting materials and new optically active carbamates as intermediates. The herbicidal activity is mainly influenced by the chiral centre, the S-isomers being the most active ones.
	Reference	Z. Naturforsch. 37b, 451—462 (1982); eingegangen am 20. August 1981
	Published	1982
	Keywords	Chloro-acetanilide, Metolachlor, Atropisomerism, Chiral Centre, Biological Activity
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	Identifier	ZNB-1982-37b-0451
	Volume	37

80	Author	A. Albini, H. Kisch, C. Krüger, An-Pei Chiang+	Requires cookie*
	Title	Transition Metal Complexes of Diazenes, XVII [1] Reactions of 1,2-Diazetines and 1,2-Diazetine-N-oxides with Iron Carbonyls
	Abstract	I,2-Diazetines, 1,2-Diazetine-N-oxide, Iron Complexes, X-ray Enneacarbonyldiiron reacts with 3,3,4,4-tetramethyl-l,2-diazetine (L) or its mono-N-oxide (L') to form complexes (L)Fe(CO)4 (3), (L)Fe2(CO)7 (4), (L)Fe2(CO)6 (5), or (L')Fe(CO)4 (6), and small amounts of deoxygenated 4 and 5, respectively. Formation and stability of the complexes is compared with those of ligands with smaller and larger ring sizes and discussed in terms of the electronic properties of the ligand lone-pair Orbitals. The molecular structure of 4 is established by X-ray analysis.
	Reference	Z. Naturforsch. 37b, 463—467 (1982); received November 13 1981
	Published	1982
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	Identifier	ZNB-1982-37b-0463
	Volume	37

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