Chelate von Chinolin-8-ol-Derivaten. XII. Die Kristall- und Molekülstruktur von Bis(7-isopropylchinolin-8-olato)nickel(II)

Chelates of 8-Quinolinol Derivatives. XII. Crystal and Molecular Structure of Bis(7-isopropyl-8-quinolinato)nickel(II) The crystal and molecular structure of bis(7-isopropyl-8-quinolinato)nickel(II) was determined by X-ray diffraction. The structure is monoclinic with the space group P2₁/n (Z = 2, 1403 observed independent reflections, R = 0.049. Lattice dimensions at 20°C: a = 1328.3(5) pm, b = 632.8(2) pm, c = 1330.0(5) pm, β = 112.99(3)°). The coordination of the nickel atom is planar with the quinoline rings in trans position.     

Zur Bestimmung von Chinosol (Kaliumsalz von 8-Hydroxychinolinsulfat)

Ohne Zusammenfassung     

Ozonolyse von Enolethern, 8. Mitteilung

Ozonolysis of Enol Ethers. Part 8. Ozonation of (1‐Methoxy‐2‐methylprop‐1‐enyl)‐1,1′‐biphenyl in Comparison with Related Oxygenations The results of conversions of 4‐(1‐methoxy‐2‐methylprop‐1‐enyl)‐1,1′‐biphenyl ( 19 ) with ozone and with dimethyldioxirane ( 6b ) under ‘normal' and ‘inverse' conditions are compared with oxygenations by dioxygen under thermal and sensitized photochemical conditions, as well as with the photooxygenation of epoxide 17 , formally derived from 19 . Ozone consumption varies between 0.7 and 1 mol‐equiv. amounts, peroxidic species are not formed. Except for bicyclus 24 , all conversions lead to mixtures of the same [1,1′‐biphenyl]‐4‐yl compounds which only differ by varying percentages. It is concluded that ozonolysis of CC bonds only represents a special type of electron‐transfer oxygenation.     

Reaktionen von LiNPPh3 mit den Cyclooctatetraenid-Komplexen [Ln(C8H8)Cl(THF)2]2 von Cer und Samarium. Die Kristallstrukturen von [LiNPPh3]6, [Ln(C8H8)Li3Cl2(NPPh3)2(THF)3] (Ln = Ce,Sm) und [Li(THF)4][Sm(C8H8)2]

Reactions of LiNPPh₃ with the Cyclooctatetraenide Complexes [Ln(C₈H₈)Cl(THF)₂]₂ of Cerium and Samarium. Crystal Structures of [LiNPPh₃]₆, [Ln(C₈H₈)Li₃Cl₂(NPPh₃)₂(THF)₃] (Ln = Ce, Sm) and [Li(THF)₄][Sm(C₈H₈)₂] LiNPPh₃ reacts with the cyclooctatetraenide complexes [Ln(C₈H₈)Cl(THF)₂]₂ of cerium and samarium in tetrahydrofuran solution forming the phosphorane iminato complexes [Ln(C₈H₈)Li₃Cl₂(NPPh₃)₂(THF)₃]. According to crystal structure analyses these complexes show heterocubane structures under participation of the lanthanoid metal atom, of the three Li atoms as well as of the two Cl und the two N atoms of the NPPh₃^– groups. The crystal structure of LiNPPh₃ shows hexameric molecules with a Li₆N₆ polyhedron which is peripherally shielded by the phenyl groups. The structure of [Li(THF)₄][Sm(C₈H₈)₂], which has been isolated as a by-product, contains the samarium atom in a sandwichlike coordination by the two η⁸-C₈H₈^2– rings as it is also known from the corresponding anions with cerium and neodymium.     

Transferreaktionen mit Hilfe von Pb(OAc)4−(CH3)3SiN3, 8. Mitt.

Zusammenfassung Es wird über das Verhalten von flexiblen Olefinen gegenüber dem Titelreagens berichtet. Anhand der aus Isobutylen, 3-Cyclohexyl-1-propen und p-Allylanisol gebildeten Reaktionsprodukte folgt, daß die Azidgruppe formal positiv übertragen wird.Cis- undtrans-Buten, Cyclohexen und Phenylcyclohexen lassen eine Präferenz dercis-Addition erkennen. Zur Erklärung des Geschehens wird ein neuer Mechanismus vorgeschlagen, der auch mit früher berichteten¹⁰ Ergebnissen vereinbar ist. Bei Styrolabkömmlingen läßt sich eine ambivalente Reaktionsweise von Pb(OAc)₄–(CH₃)₃Sin₃ erkennen.

---

Transfer reactions by means of Pb(OAc)₄–(CH₃)₃SiN₃

The behaviour of flexible olefins with the title reagent is studied. By means of the reaction products of isobutylene, 3-cyclohexyl-1-propene and p-allylanisole it is shown that the transfer process can be envisaged as being realized by formally positive azide.Cis- andtrans-butene, cyclohexene and phenylcyclohexene favourcis-addition. A new mechanistic interpretation is presented, which is in accord with earlier results. With styrene derivatives an ambivalent behaviour occurs.

---

---

Mit 1 Abbildung     

Die Reaktionen von Gallium, Indium und Thallium(in) mit Thiooxin-(8-Mercaptochinolin)

Ohne Zusammenfassung     

Zur Umsetzung von 3,4-Dihydro-8a-methoxy-2H-1,4-benzoxazin-6(8aH)-onen mit Diazoalkanen, 1. Mitt.

Summary 3,4-Dihydro-8a-methoxy-2H-1,4-benzoxazin-6(8aH)-ones — quinol derivatives of 2-hydroxyethylamino-1,4-benzoquinones — react with diazoalkanes to yield 2,3,9a,9b-Tetrahydro-9H-pyrazolo[3,4-h]-1,4-benzoxazin-6(6aH)-ones (3). Their structures were established on basis of NMR-techniques including two-dimensional experiments. The orientation phenomena of the reaction is discussed.

     

Zur Umsetzung von 8a-Methoxy-3,4-dihydro-2H-1,4-benzoxazin-6(8aH)-onen mit Diazoalkanen, 2. Mitt.

Summary 8a-Methoxy-3,4-dihydro-2H-1,4-benzoxazin-6(8aH)-ones2 undergo regio- and stereospecific 1,3-dipolar cycloaddition reactions with diazomethane or diazoethane to yield 3,4,6a,9,9a,9b-hexahydro-pyrazolo[3,4-h][1,4]benzoxazin-6(2H)-ones3, which slowly isomerize in solution to give the 3,4,8,9,9a,9b-hexahydro-pyrazolo[3,4-h][1,4]benzoxazin-6(2H)-ones5. The carbon of the diazoalkane dipole is attached to carbon C-8 of the benzoxazinone. The structures of the obtained products were determined by¹H- and¹³C-NMR spectroscopy. An X-ray crystal structure analysis of3 a was carried out at room temperature:C₁₁H₁₅N₃O₃,M _r =237.26, orthorhombic, Pc2₁n,a=9.173 (5),b=9.133 (4),c=13.281 (6),V=1112.6 (9) ų,Z=4,d _x =1.416 g/cm^–3, =0.93 cm^–1,R=4.33%,R _w =3.95% (919 observations, 168 parameters).

Herrn Prof. Dr. W. Fleischhacker zum 60. Geburtstag gewidmet     

Die Bildung von Mischliganden-Komplexen bei der Extraktion von Zink in Gegenwart von 8-Hydroxychinolin (ox) und 1,10-Phenanthrolin (phen)

Ohne Zusammenfassung     

Photochemische Reaktionen. 39. Mitteilung. Photochemische Umwandlungen von endo-Tricyclo[4.3.12,5.0]-decadien-(3,8)-dion-(7,10) und cis-8, 9-Dihydroindenon

In boiling xylene the cyclopentadienedione 1 is thermally decarbonylated to cis-8,9-dihydroindenone ( 8 ). This method avoids secondary reactions and allows the preparation of 8 in high yield.     

Umsetzungen von Allyldichlorphosphit und Allyldifluorphosphit mit einigen Verbindungen von Übergangsmetallen; Darstellung und spektroskopische Untersuchung von Allyldichlor- bzw. Allyldifluorphosphit-Carbonyl-Metall(0)-Koordinationsverbindungen (MetallCr,Mo, W,Fe)

Reactions of Allyldichlorophosphite and Allyldifluorophosphite with some Transition Metal Compounds; Synthesis and Spectroscopic Identification of Allyldichloro- and Allyldifluorophosphite-Carbonyl-Metal(0) Coordination Compounds (Metal?Cr, Mo, W, Fe) In the reactions of allyldifluorophosphite ( 1 ) and allyldichlorophosphite ( 2 ) with the carbonyl compounds (C₇H₈)M(CO)₃ (M?Cr, Mo; C₇H₈ ? cycloheptatriene), W(CO)₅THF (THF = tetrahydrofuran), Fe(CO)₅ or Fe₂(CO)₉ the allyldichloro- and allyldifluorophosphite-carbonyl-metal compounds fac-(AllOPF₂)₃Cr(CO)₃ 3 a , mer-(AllOPF₂)₃Cr(CO)₃ 3 b , fac-(AllOPF₂)₃Mo(CO)₃ 4 , fac-(AllOPCl₂)₃Mo(CO)₃ 5 , (AllOPF₂)W(CO)₅ 6 , (AllOPCl₂)W(CO)₅ 7 , (AllOPF₂)Fe(CO)₄ 8 and (AllOPCl₂)Fe(CO)₄ 9 were formed (All = CH₂?CHCH₂). In 8 and 9 the ligands 1 or 2 are axially orientated. The validity of the concept of hard and soft acids and bases (HSAB-concept) and of the 18-valency electron rule (18-VE-rule) was confirmed. The allyl dihalophosphites 1 and 2 coordinate via phosphorus. The allylic π-system was not involved in the coordinative bond. The characterization of the coordination compounds 3 , 4 , 5 a , 5 b und 6 ? 9 was based on their IR and NMR spectra, and on the mass spectra.     

Spektralphotometrische Bestimmung von Chrom(VI) und Vanadium(V) mit 8-Aminochinolin

Ohne Zusammenfassung     

Eine spektrophotometrische Bestimmung von 8-Hydroxypenicillins?ure (HPS)

Ohne Zusammenfassung     

Zur Darstellung von Yttriumhydridhalogeniden YXHn (X  Cl,Br)

On the Preparation of Yttrium Hydride Halides YXH_n (X ? Cl, Br) The compounds YCl and YBr described in a previous paper as “monohalides” in reality are hydridehalides YClH_n and YBrH_n with the H-concentration in the range 0.7 ≤ n ≤ 1.0. Dehydrogenation experiments on YCIH_0.7 in all cases resulted in heterogeneous products consisting of YCl₃, Y and YClH_n. With increasing hydrogen content the c-lattice parameter decreases. Observed minimal c-lattice parameter is 2727.0(7) pm (for n ≈? 1), maximum c-lattice parameter is 2752.3(4) pm (for n ≈? 0.68). YBrH_n crystallizes in the ZrBr-structure type, YClH_n for 0.7 ≤ n ≤ 0.8 in the ZrBr-type, for 0.8 ≤ n ≤ 1.0 in the ZrCl-type. YXH_n (X ? Cl, Br) has a graphite like colour and in H atmosphere can be hydrogenated to the colourless compound YXH₂. YClH₂ and YBrH₂ are isotypic with TbBrD₂. A miscibility gap was found between YClH_1.0 and YClH_2.0.     

Unique [(1)infinityNi(8)Bi(8)S] metallic wires in a novel quasi-1D compound. Synthesis, crystal and electronic structure, and properties of Ni(8)Bi(8)SI.

A new quasi-one-dimensional compound Ni(8)Bi(8)SI has been synthesized and its crystal structure determined from single-crystal X-ray diffraction data. The structure of Ni(8)Bi(8)SI consists of [(1)infinityNi(8)Bi(8)S] columns separated by iodine atoms. Conductivity and magnetic susceptibility measurements (down to 4.2 K) show that Ni(8)Bi(8)SI is a one-dimensional metal and exhibits Pauli paramagnetic properties. These observations are in good agreement with the results from electronic structure calculations. An analysis of the chemical bonding employing difference electron charge density maps reveals strong multicenter Ni-Bi bonds and pair Ni-S interactions within the [(1)infinityNi(8)Bi(8)S] columns. Only electrostatic interactions are inferred between the columns and iodine atoms.     

Die Kristallstruktur von Cs5Eu(N3)8

Summary The crystal structure of pentacesium octaazidoeuropiate(III), Cs₅Eu(N₃)₈, was determined by single crystal X-ray diffraction: orthorhombic,a=16.811(4),b=16.860(5),c=16.964(3)Å, space group Pbca,Z=8, 2 310 observed reflections,R=0.048. Europium atoms are coordinated to eight azide groups, the coordination polyhedra have no azide groups in common. Four cesium atoms are surrounded by eight, one by seven azide groups. The azide groups are symmetric with mean N-N-distances of 1.17(1)Å.