Karl-Friedrich Tebbe

Über Kalium-Benzo-18-Krone-6-Polyiodide [K(Benzo-18-Krone-6)]Inmit n = 3, 4, 6: Darstellung und strukturelle Charakterisierung eines Triiodids [K(Benzo-18-Krone-6)]I3, eines Oktaiodids [K(Benzo-18-Krone-6)]2I8 · 1/2C2H5OH und eines Dodecaiodids [K(Benzo-18-Krone-6)]2I12

Die bisher unbekannten Verbindungen [K(Benzo-18-Krone-6)]I3, [K(Benzo-18-Krone-6)]2I8 · 1/2 C2H5OH und [K(Benzo-18-Krone-6)]2I12 fallen bei der Umsetzung von Benzo-18-Krone-6 (B18K6, C16H24O6), Kaliumiodid KI und Iod I2 in Ethanol/Dichlormethan aus. Die Kristallstrukturen wurden mit Rontgenbeugungsmethoden an Einkristallen bestimmt. Das Triiodid enthalt jeweils zwei kristallographisch verschiedene Kationen [K(Benzo-18-Krone-6)]+ und Anionen I3–, die als isolierte Einheiten vorliegen. Im Oktaiodid und im Dodecaiodid sind die Polyiodid-Ionen in ein I3–- und ein I5–-Ion bzw. in ein I5–- und ein I7–-Ion gespalten. Das Oktaiodid bildet einen bisher noch nicht beschriebenen neuen Kettentyp mit einer zusatzlichen zweifachen Koordination uber das mittlere der drei Triiodid-Atome. Im Dodecaiodid bilden die Z-formigen Heptaiodid-Einheiten eine Helix, die durch die V-formigen Pentaiodid-Einheiten begrenzt wird. Studies of Polyhalides. 38. On Potassium-Benzo-18-Crown-6-Polyiodides [K(benzo-18-crown-6)]In with n = 3, 4, 6: Preparation and Crystal Structures of a Triiodide [K(benzo-18-crown-6)]I3, an Octaiodide [K(benzo-18-crown-6)]2I8 · 1/2C2H5OH and a Dodecaiodide [K(benzo-18-crown-6)]2I12 The new compounds [K(benzo-18-crown-6)]I3, [K(benzo-18-crown-6)]2I8 · 1/2 C2H5OH, and [K(benzo-18-crown-6)]2I12 have been prepared by the reaction of benzo-18-crown-6 (B18K6, C16H24O6), potassium iodide KI and iodine I2 in ethanol/dichlormethane. Their crystal structures have been determined by single crystal X-ray diffraction methods. The triiodide consists of two crystallographically different cations [K(benzo-18-crown-6)]+ and anions I3– respectively, which can be regarded as isolated units. The octaiodide and the dodecaiodide achieve their structure by a decomposition into a I3–- and a I5–-ion or a I5–- and a I7–-ion. The octaiodide builds a new type of chain with an additional twofold co-ordination via the middle iodine atom of the triiodide group. This type of chain has not been described up to now. In the dodecaiodide the Z-shaped heptaiodide units form a helix which is limited by the V-shaped pentaiodide units.

Synthesen und Eigenschaften von Pentafluorethylkupfer(I)‐ und ‐(III)‐Verbindungen: Cu(C2F5) · D, [Cu(C2F5)2]– und (C2F5)2CuSC(S)N(C2H5)2

Cd(C2F5)2 · D bzw. Zn(C2F5)2 · D (D = 2 CH3CN, 2 DMF) reagieren mit Kupfer(I)halogeniden in Gegenwart von Halogeniden quantitativ zu den CuC2F5-Verbindungen CuC2F5 · D und [Cu(C2F5)2]–. Die CuC2F5-Komplexe werden NMR-spektroskopisch identifiziert, [Cu(C2F5)2]– wird als PNP-Salz (PNP = (C6H5)3PNP(C6H5)3+) isoliert. Beide Pentafluorethylkupfer(I)-Verbindungen sind bei tiefer Temperatur sehr reaktive Pentafluorethylierungs-Reagenzien. Die Oxidation von [Cu(C2F5)2]– mit [(C2H5)2NC(S)S]2 ergibt die kristalline Cu(III)-Verbindung (C2F5)2CuSC(S)N(C2H5)2 (monoklin, C2/c). Syntheses and Properties of Pentafluoroethylcopper(I) and -copper(III) Compounds: CuC2F5 · D, [Cu(C2F5)2]–, and (C2F5)2CuSC(S)N(C2H5)2 The reactions of Cd(C2F5)2 · D and Zn(C2F5)2 · D (D = 2 CH3CN, 2 DMF), respectively, with copper(I) halides in the presence of halides quantitatively yield the CuC2F5 compounds CuC2F5 · D and [Cu(C2F5)2]–. The CuC2F5 complexes are identified by NMR spectroscopy, while [Cu(C2F5)2]– is isolated as PNP salt (PNP = (C6H5)3PNP(C6H5)3+). Both compounds are excellent C2F5 group transfer reagents, even at low temperature. Oxidation of [Cu(C2F5)2]– with [(C2H5)2NC(S)S]2 yields the crystalline Cu(III) compound (C2F5)2CuSC(S)N(C2H5)2 (monoclinic, C2/c).

[Ba(Benzo-15-Krone-5)2](In)2: Darstellung und strukturelle Charakterisierung eines Triiodids (n = 3) und eines Heptaiodids (n = 7)

[Ba(benzo-15-crown-5)2](I3)2 and [Ba(benzo-15-crown-5)2](I7)2 can be obtained in crystalline form by reacting benzo-15-crown-5 (C14H20O5), barium iodide (BaI2), and iodine (I2) in ethan-ole /dichloromethane. The triiodide consists of a sandwich-like cation [Ba(benzo-15-crown-5)2]2+ and an isolated symmetrically linear I3- anion. The unusual I7- anion in the heptaiodide can be described as a V-shaped pentaiodide unit, which is connected with a slightly widened iodine molecule to the rare Z-form of the heptaiodide ion. In the crystal structure, secondary bonding distances lead to almost planar ten-membered iodine rings, which are connected by common edges to form staircase-like bands.

Über die Decamethylferroceniumpolyiodide [(Me5C5)2Fe]Ix mit x = 3, 5 und 6,5. Darstellung und strukturelle Charakterisierung eines Triiodids (DMFc)I3, eines Pentaiodids (DMFc)I5 und eines Hexacosaiodids (DMFc)4I26

Ahnlich dem Ferrocen (Fc) selbst last sich Decamethylferrocen (DMFc) mit Iod zum Decamethylferrocenium-Ion (DMFc)+ oxidieren und schrittweise in die kristallinen Festkorper Decamethylferroceniumtriiodid (DMFc)I3, Decamethylferroceniumpentaiodid (DMFc)I5 und Tetrakisdecamethylferroceniumhexacosaiodid (DMFc)4I26 uberfuhren, von denen die iodreicheren Verbindungen neu sind. Hiervon wurden Kristallstrukturanalysen mit Rontgenbeugungsmethoden angefertigt, die neben dem komplexen Kation der erwarteten Struktur isolierte oder bemerkenswert vernetzte Polyiodid-Ionen enthalten. Decamethylferroceniumtriiodid C20H30FeI3 kristallisiert in der monoklinen Raumgruppe C2/m mit a = 1489,9(4) pm, b = 1133,0(2) pm, c = 765,9(3) pm, β = 111,76(3)° und Z = 2. Die Kristallstruktur folgt dem CsCl-Typ und enthalt isolierte gestreckt symmetrische Triiodid-Ionen. Decamethylferroceniumpentaiodid C20H30FeI5 kristallisiert in der monoklinen Raumgruppe P21/c mit a = 1130,0(2) pm, b = 1442,6(1) pm, c = 1716,6(2) pm, β = 96,62(1)° und Z = 4. Die Kristallstruktur last sich aus der primitiv quadratischen Saulenbundelung wechselnd kationischer und anionischer Stabe herleiten und enthalt eher selten beobachtete isolierte, leicht gespreizte Pentaiodid-Ionen. Tetrakisdecamethylferroceniumhexacosaiodid (C20H30Fe)4I26 kristallisiert in der monoklinen Raumgruppe P21/n mit a = 1331,3(8) pm, b = 1319,4(4) pm, c = 3564(2) pm, β = 90,84(5)° und Z = 2. Die Kristallstruktur dieser ungewohnlich zusammengesetzten Verbindung erweist sich als Kanal-Einschlusverbindung, deren bisher einzigartiges anionisches Raumnetz sich aus dem langs samtlicher Wurfelkanten durch Iodmolekule verbruckten kubisch primitiven Iodid-Gitter durch systematisches Entfernen von 1/12 der Iodmolekule herleiten last. Studies on Polyhalides. 30 On Decamethylferriciniumpolyiodides [(Me5C5)2Fe]Ix with x = 3, 5, 6.5: Preparation and Crystal Structures of a Triiodide (DMFc)I3, a Pentaiodide (DMFc)I5 and a Hexacosaiodide (DMFc)4I26 Decamethylferrocene (DMFc) may be oxidized by iodine analogous to ferrocene (Fc) to the decamethylferrocenium ion (DMFc)+ and precipitated as the crystalline solids decamethylferrocenium triiodide (DMFc)I3, decamethylferrocenium pentaiodide (DMFc)I5 and tetracisdecamethylferrocenium hexacosaiodide (DMFc)4I26. The two compounds with higher iodine content are new. These are characterized by X-ray diffraction methods on single crystals. The structures are built up from complex cations of expected geometry and isolated or remarkably connected polyiodide ions. Decamethylferrocenium triiodide C20H30FeI3 crystallizes monoclinically in C2/m with a = 1489.9(4) pm, b = 1133.0(2) pm, c = 765.9(3) pm, β = 111.76(3)° and Z = 2. The crystal structure follows the CsCl-type and contains isolated triiodide ions of the linear symmetric form. Decamethylferrocenium pentaiodide C20H30FeI5 crystallizes monoclinically in P21/c with a = 1130.0(2) pm, b = 1442.6(1) pm, c = 1716.6(2) pm, β = 96.62(1)° and Z = 4. The crystal structure may be deduced from the primitiv quadratic bundle of alternating cationic and anionic rods. It contains exceptionally isolated somewhat opened out pentaiodide ions. Tetrakisdecamethylferrocenium hexacosaiodide (C20H30Fe)4I26 crystallises monoclinically in P21/n with a = 1331.3(8) pm, b = 1319.4(4) pm, c = 3564(2) pm, β = 90.84(5)° and Z = 2. The crystal structure of this compound with unusual composition may be described as an inclusion compound with channels for the cations. The outstanding anionic grating may be derived from the primitive cubic lattice of iodide ions with iodine bridges on all edges by removing systematically 1/12 of the iodine molecules.

Untersuchungen an Polyhalogeniden, XXXXII [1]. Das Pentaiodid-Ion I5-; Eine Übersicht: Darstellung und Kristallstruktur der Verbindung [Rb(C16H24O6)](I5) · H2O

Abstract [Rb(benzo-18-crown-6)](I5) H2O could be prepared by the reaction of benzo-18-crown-6, rubidium iodide, and iodine in ethanol / dichloromethane. It crystallizes in the monoclinic space group P21/a with a = 1881.8(3), b = 1439.0(2), c = 2269.0(3) pm, ß = 111.24(1)° and Z = 8. The crystal structure was refined to RF = 0.038 for 5310 reflections. It contains two independent molecules. The two cations and the coordinating water molecules form a zigzag chain running along [100] paralleled by two structurally similar pentaiodide chains with one leg of the V-shaped pentaiodide ion forming the backbone of the chain. In both cases the other leg stands out in a novel fashion without forming a coplanar cis or trans configuration known from other pentaiodides. Anionic motifs of other crystalline pentaiodides are summarized and discussed.

Ethyltrimethylammoniumpentaiodid (EtMe3N)I5

(EtMe3N)I5 wurde durch Umsetzung stochiometrischer Mengen von Ethyltrimethylammoniumiodid und Iod in Methanol gewonnen. Sie kristallisiert in der orthorhombischen Raumgruppe Pna21 mit a = 1011,3(1) pm, b = 1255,3(2) pm, c = 1237,7(2) pm und Z = 4. Die anionische Iod-Teilstruktur setzt sich aus gewellten Schichten zusammen, die sich durch Deformation des ebenen quadratischen Netzes mit Iodid-Ionen in den Knoten und Iodmolekulen auf den Seiten der Maschen ergeben. Studies on Polyhalides. 40. Ethyltrimethylammonium Pentaiodide (EtMe3N)I5 (EtMe3N)I5 has been prepared by the reaction of stoichiometric amounts of ethyltrimethylammonium iodide and iodine in methanol. It crystallizes in the orthorhombic space group Pna21 with a = 1011.3(1) pm, b = 1255.3(2) pm, c = 1237.7(2) pm and Z = 4. The anionic iodine partial structure is composed of puckered layers which may be derived by deforming a quadratic net with iodide ions in the knots and iodine molecules on the edges of the meshes.

Untersuchungen an Polyhalogeniden, XXXIV Cäsium(18-Krone-6)dichloroiodat, [Cs(C12H24O6)]ICl2/Studies on Polyhalides, XXXIV Cesium (18 -crown -6 )dichloroiodate, [Cs(C12H24O6)]ICl2

Abstract The new compound [Cs(18-crown-6)]ICl2 has been prepared by the reaction of cesium chloride and 18-crown-6 with iodine chloride in ethanol and structurally characterized by X-ray diffraction methods. The geometries of the cation [Cs(18-crown-6)]+ and of the anion ICl2- are as expected.

Untersuchungen an Polyhalogeniden, XII [1] Darstellung und Kristallstruktur von [K(Crypt-2.2.2)]l2I12 / Studies on Polyhalides, XII [1] / Preparation and Crystal Structure of [K(Crypt-2.2.2)]2I12

The new compound [K(Crypt-2.2.2)]2I12 has been prepared by the reaction of [K(Crypt-2.2.2)]I with iodine in a mixture of ethanol and dichloromethane. It crystallizes in the triclinic space group PĪ with a = 1201,5(5), b = 1213,4(5), c = 1432,1(2) pm, α = 69,11(2), β = 72,01(2), γ= 61,93(3) and Z = 1. The crystal structure has been refined to RF = 0.030 for 2882 reflections. The structure may be described as a layerlike packing of I122- anions and [K(Crypt-2.2.2)]+ cations. The anion with point symmetry Ci consists of two pentaiodide groups and a bridging iodine molecule.

Beiträge zur Strukturchemie phosphorhaltiger Ketten und Ringe

The bicyclic phosphorus compound 2,3,4,6-Tetra-ter/-butylbicyclo[3.1.Ojhexaphosphane í-Bu4P6, C 1 6H 3 6P 6 crystallizes in the monoclinic space group P2Jn with a = 912.0pm, 6 = 1383.8pm, c= 1951.4pm, β = 90.93° and Ζ = 4 formula units. The crystal structure has been worked out by single crystal X-ray methods and refined to R = 0.045 with 860 observed reflections. The molecule consists of a three-membered phosphorus ring connected to a five-membered ring by a common edge. The bicyclus has a chair-like phosphorus skeleton. The slightly distorted three-membered ring stands almost perpendicular to the five-membered ring. The latter adopts the conformation of an unusually flat, only slightly twisted envelope. The common edge with d (Ρ—P) = 219.7 pm and the average endocyclic bonding distance ¿(P — P) = 219.9 pm in the five-membered ring are almost equal, but different from the average endocyclic bonding distance <?(P—P) = 218.3 pm in the three-membered ring. The arrangement of the substituents tert-butyl is all-trans. The average bond lengths rf(P—C) = 190.4 pm and d(C — C) = 152.4 pm are as expected.

Li3Al2, eine neue Phase im System Li/Al / Li3Al2, a New Phase in the System Li/Al

Besides ‘Li2Al’ which was recently shown to be the phase Li9Al4 there exists the phase Li3Al2 characterized by preparation and X-ray diffraction methods. It cristallizes with a rhomboedric unit cell, R3̄m, a = 4.508 Å, c = 14.26 Å and z = 3 formula units (hexagonal setting). The structure can be looked at as a variant of the body centred cubic packing with Αl-atom layers of puckered six membered rings. The structural relation of the phases LiAl, Li3Al2, Li9Al4, Li is discussed.