FU Berlin Digitale Dissertation
Stephan Sommer : Synthesis and structures of iodo-d10-metallates(I) with chiral kations Synthesen und Strukturen von Iodo-d10-metallaten(I) mit chiralen Kationen
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Abstract Trying to examine the influence of chirality of cations on the formation of iodocuprate(I) and iodoargentate(I) anions in the reaction of chiral cations with copperiodine or silveriodine one can find some new, partly chiral iodocuprates(I) and iodoargentates(I). It was possible to determine the structures by X-ray methods. The chiral pentagonal bipyramidal anion [Cu5I7 · 2 CH3CN]2- can be found with one enantiomorph of a cation. It was also possible to determine the structure of the chiral anion ¥1[Cu5I7]2-, in which pentagonal bipyramids form a helical chain. This structure can be interpreted as the polymerization product of the [Cu5I7 · 2CH3CN]2- anion by loss of the acetonitrile ligands and using iodine of the pentagonal basis of neighbouring bipyramids instead. The two enantiomorphs of an interesting chiral 3-dimensional structure [Ag6I8]2- can be received as products of the reaction of silveriodine with the enantiomorphs of (1-Phenyl-ethyl)trimethylammoniumiodine. The network is built of pentagonal Ag5I7 bipyramids connected directly (sharing edges of the pentagonal basis) and using the AgI, which takes not part in the formation of the pentagonal bipyramids, containing the cations in the resulting cylindrical cavities. One can suppose properties of a solid electrolyte considering the structure of these both anions with face-sharing occupied and unoccupied tetrahedrons. An astonishing fact is the crystallization of a totally different anion using the racemic cation. In this case an ¥1[AgI2]- anion (SiS2-type) appeared and the same effect using CuI instead of AgI (¥1[CuI2]- with the racemic cation and chiral [Cu5I7 · 2 CH3CN]2- with the enantiomorphs). The reactions of the other chiral cations used in the reaction with silveriodine only lead to the non-chiral anion ¥1>[Ag2I3]-, the most common anionic configuration of iodoargentates(I). As byproducts of the reaction of AgI with chiral cations two uncommon iodoargentates (I) with solvated Ag+ cations can be determined. Chirality of the cations seems not to be the only factor that influences the formation of iodocuprate(I) and iodoargentate(I) anions. Also the size, the shape and the distribution of the positive charge of the cations have influence on the resulting anions explaining the formation of different structures using similar cations. The striking problem in this system is the crystallization and the reproduction of the species. The crystal growth is very sensitive to insignificant changes of the reaction conditions and this sensitivity is even higher using chiral substances. We observed this known phenomena especially in the reactions with CuI, where we suppose the existence of the chiral anion [Cu5I7 · 2 CH3CN]2- in solution, as opposed to the reactions with AgI (analogous chiral anion [Ag5I7 · 2 CH3CN]2- unknown). Two new Bromocuprates have been prepared and characterized examining the paticipation of halogenocuprates(I) in the Sandmeyer reaction. Both, one with an isolated [CuIIBr4]2- anion and the second with the ¥1[Cu5Br8]3- anion, a chain of pentagonal Cu5Br7 bipyramids connected via the 8th Br, represent only intermediate byproducts and not "reactive" intermediates of the Sandmeyer reaction. As a result of this work one can establish that in the system of halogeno-d10-metallates the "uncommon" anionic configuration of pentagonal bipyramids appears frequently. The pentagonal bipyramid represents a part of a room-centered icosahedron. This is very similar to a room-centered cuboctahedron, the characteristic of a cubic closest package of spherical particles of the same size. This close or nearly closest package of the halogene atoms with the metal atoms in the tetrahedral holes seems to be the motive power to build the pentagonal bipyramidal configuration in the halogeno-d10-metallate anions.

Table of Contents Download the whole PhDthesis as a zip-tar file or as zip-File For download in PDF format click the chapter title Titel     Inhaltsverzeichnis   1. Einleitung 4 1.1 Halogeno-d10-metallate 4 1.2 [Cu5I7 · 2 CH3CN]2- und ¥1[Cu3I4]- als chirale Anionen 5 1.3 Iodoargentat(I)-Verbindungen 7 1.4 Zielsetzung 7       2. Untersuchungsmethoden 8       3. Chirale Kationen 11 3.1 (1-Phenylethyl)trimethylammoniumiodid 12 3.1.1 Darstellung von (1-Phenylethyl)trimethylammoniumiodid 12 3.1.2 Charakterisierung von (1-Phenylethyl)trimethylammoniumiodid 12 3.2 (1-Cyclohexylethyl)trimethylammoniumiodid 13 3.2.1 Darstellung von (1-Cyclohexylethyl)trimethylammoniumiodid 13 3.2.2 Charakterisierung von (1-Cyclohexylethyl)trimethylammoniumiodid 14 3.3 (2-Hydroxy-1-methyl-2-phenylethyl)trimethylammoniumiodid 17 3.3.1 Darstellung von (2-Hydroxy-1-methyl-2-phenylethyl)trimethylammoniumiodid 17 3.3.2 Charakterisierung von (2-Hydroxy-1-methyl-2-phenylethyl)trimethyl-ammoniumiodid 18 3.4 (1-(1-Naphthyl)ethyl)trimethylammoniumiodid 24 3.4.1 Darstellung von (1-(1-Naphthyl)ethyl)trimethylammoniumiodid 24 3.4.2 Charakterisierung von (1-(1-Naphthyl)ethyl)trimethylammoniumiodid 24 3.5 Zusammenfassende Übersicht über die dargestellten chiralen Kationen 25       4. Umsetzungen von Kupferiodid mit chiralen Kationen 26 4.1 Umsetzungen mit (1-Phenylethyl)trimethylammoniumiodid 27 4.1.1 Bis-(R)-(1-Phenylethyl)trimethylammoniumheptaiodopentacuprat(I) · 3 CH3CN [(R)-C11H18N]2[Cu5I7 · 2 CH3CN] · CH3CN 27 4.2 Umsetzungen mit (1-Cyclohexylethyl)trimethylammoniumiodid 33 4.2.1 Bis-(R/S)-(1-Cyclohexylethyl)trimethylammoniumtetraiododicuprat(I) [(R/S)-C11H24N]2[Cu2I4] 33 4.3 Umsetzungen mit (2-Hydroxy-1-methyl-2-phenylethyl)trimethylammoniumiodid 37 4.3.1 Bis-(+)-(2-Hydroxy-1-methyl-2-phenylethyl(trimethylammoniumheptaiodo-pentacuprat(I) [(+)-C12H20NO]2 ¥1[Cu5I7] 39 4.4 Umsetzungen mit (1-(1-Naphthyl)ethyl)trimethylammoniumiodid 45 4.5 Ergebnisse aus den Umsetzungen mit Kupferiodid 45       5. Umsetzungen von Silberiodid mit chiralen Kationen 47 5.1 Umsetzungen mit (1-Phenylethyl)trimethylammoniumiodid 47 5.1.1 (R/S)-(1-Phenylethyl)trimethylammoniumdiiodoargentat(I) [(R/S)-C11H18N] ¥1[AgI2] 48 5.1.2 Bis-(R)-(1-Phenylethyl)trimethylammoniumoctaiodohexaargentat(I) [(R)-C11H18N]2 ¥3[Ag6I8] 52 5.1.3 Bis-(S)-(1-Phenylethyl)trimethylammoniumoctaiodohexaargentat(I) [(S)-C11H18N]2 ¥3[Ag6I8] 59 5.2 Umsetzungen mit (1-Cyclohexylethyl)trimethylammoniumiodid 63 5.2.1 (R)-(1-Cyclohexylethyl)trimethylammoniumtriiododiargentat(I) [(R)-C11H24N] ¥1[Ag2I3] 63 5.2.2 (S)-(1-Cyclohexylethyl)trimethylammoniumtriiododiargentat(I) [(S)-C11H24N] ¥1[Ag2I3] 65 5.2.3 Produkte aus der Umsetzung mit (R/S)-(1-Cyclohexylethyl)trimethyl-ammoniumiodid 67 5.3 Umsetzungen mit (2-Hydroxy-1-methyl-2-phenylethyl)trimethylammoniumiodid 68 5.3.1 (+)-(2-Hydroxy-1-methyl-2-phenylethyl)trimethylammoniumtriiododiargentat(I) [(+)-C12H20NO] ¥1[Ag2I3] 69 5.3.2 (-)-(2-Hydroxy-1-methyl-2-phenylethyl)trimethylammoniumtriiododiargentat(I) [(-)-C12H20NO] ¥1[Ag2I3] 71 5.3.3 Produkte aus der Umsetzung mit (+/-)-(2-Hydroxy-1-methyl-2-phenyl-ethyl)-trimethylammoniumiodid 73 5.4 Umsetzungen mit (1-(1-Naphthyl)ethyl)trimethylammoniumiodid 73 5.4.1 (S)-(1-(1-Naphthyl)ethyl)trimethylammoniumtriiododiargentat(I) [(S)-C14H18N] ¥1[Ag2I3] 74 5.5 Nebenprodukte bei den Umsetzungen von Silberiodid mit chiralen Kationen 80 5.5.1 Kristallstruktur von Disilbertriiodoargentat(I) Ag2 ¥1[AgI3] · x CH3CN 80 5.5.2 Kristallstruktur von Silberdiiodoargentat(I) Ag ¥1[AgI2] · ½ CH3CN 82 5.6 Ergebnisse aus den Umsetzungen mit Silberiodid 85       6. Halogenocuprat(I)-Verbindungen als Zwischenstufen der Sandmeyer-Reaktion 87 6.1 Die Sandmeyer-Reaktion 87 6.2 Versuch der Isolierung von kristallinen Zwischenstufen 92 6.2.1 Tris(4-Methylphenyldiazonium)octabromopentacuprat(I) [C7H7N2]3 ¥1[Cu5Br8] 94 6.2.2 Bis(4-Methylphenyldiazonium)tetrabromocuprat(II) [C7H7N2]2 [CuBr4] 97 6.3 Ergebnisse der Untersuchungen zur Beteiligung von Halogenocupraten(I) an der Sandmeyer-Reaktion 99       7. Zusammenfassung 101       8. Abstract 104       9. Anhang 107 9.1 Anhang A ? Kristallografischer Teil 107 9.2 Anhang B ? Kernresonanz-Spektren 164 9.3 Anhang C ? Verwendete Chemikalien 169       10. Literaturverzeichnis 170         Lebenslauf

More Information:
Online available:	http://www.diss.fu-berlin.de/2001/1/indexe.html
Language of PhDThesis:	german
Keywords:	halogenocuprates, halogenoargentates, chirality
DNB-Sachgruppe:	30 Chemie
Date of disputation:	09-Nov-2000
PhDThesis from:	Fachbereich Biologie, Chemie, Pharmazie, Freie Universität Berlin
First Referee:	Prof. Dr. Hans Hartl
Second Referee:	Prof. Dr. Ulrich Abram
Contact (Author):	sose@chemie.fu-berlin.de
Contact (Advisor):	hartl@chemie.fu-berlin.de
Date created:	02-Jan-2001
Date available:	05-Jan-2001

 

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