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  • 1
    ISSN: 0044-2313
    Keywords: (1,2-dimethoxyethane-O,O′)lithium methylphosphanide ; (2,5,8-trioxanonane-O2,O5)lithium methylphosphanide ; catena-poly(lithium-organylphosphanide) ; X-ray structure determination ; meso-helix ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Derivatives of Molecular Compounds. VIII. catena-Poly[(2,5,8-trioxanonane-O2,O5) lithium-methylphosphanide]  -  a Compound with a meso-Helix StructureStudies of Fritz et al. [10] showed methylphosphane to be lithiated at -60°C in 1,2-dimethoxyethane or bis(2-methoxyethyl) ether solution by stoichiometric amounts of lithium n-butanide in n-hexane. After removing the hydrocarbons almost completely by distillation and cooling the solutions to -60°C again, colourless square crystals of (1,2-dimethoxyethane-O,O′)lithium (1) and (2,5,8-trioxanonane-O2,O5)lithium methylphosphanide (2) precipitate. As shown by an X-ray structure determination (monoclinic, P21/n; a = 805.5(1); b = 1820.6(2); c = 851.5(1) pm; β = 116.76(1)° at -100 ± 3°C; Z = 4 formula units; R = 0.034) complex 2 forms a polymer which has the shape of an up to now scarcely noted meso-helix. Four-coordinated lithium is bound to two phosphorus (P—Li 252.9 and 253.2 pm; P—Li—P 131.8°; Li—P—Li 132.1°) and to two oxygen atoms (Li—O 203.9 and 206.8; O … O 270.7 pm; O—Li—O 82.5°) of the inherently tridentate 2,5,8-trioxanonane ligand. As compared to the standard value (185 pm) the P—C distance (187.4 pm) is slightly lengthened. Structure determinations of (2,5,8-trioxanonane-O2,O5,O8) lithium 1-(phenylsulfonyl)alkyl compounds published some years ago [26, 27], allow a comparison of molecular parameters characteristic for the twofold or threefold coordinating chelate ligand.
    Notes: Nach Untersuchungen von Fritz u. a. [10] wird in 1,2-Dimethoxyethan oder Bis(2-methoxyethyl)ether Zur einfacheren Beschreibung der Koordination am Lithium wählen wir beim Bis(2-methoxyethyl)ether (diglyme) das Synonym 2,5,8-Trioxanonan. 1,2-Bis(dimethylamino)ethan (tmeda), Tetrahydrofuran (thf), 1,2-Dimethoxyethan (dme), Diethylether (OEt2) gelöstes Methylphosphan bei -60°C durch Lithium-n-butanid in n-Hexan metalliert. Beim Abkühlen der von Kohlenwasserstoffen weitgehend befreiten Ansätze auf wiederum -60°C kristallisiert (1,2-Dimethoxyethan-O,O′)lithium- (1) bzw. (2,5,8-Trioxanonan-O2,O5) lithium-methylphosphanid (2) in farblosen Quadern aus. Nach einer Röntgenstrukturanalyse (monoklin, P21/n; a = 805,5(1); b = 1 820,6(2); c = 851,5(1)pm; β = 116,76(1)° bei -100 ± 3°C; Z = 4 Formeleinheiten; R = 0,034) liegt Komplex 2 als Polymer in der bislang wenig beachteten achiralen Abfolge einer „meso-Helix“ vor. Lithium weist mit Bindungen zu zwei Phosphor- (P—Li 252,9 und 253,2 pm; P—Li—P 131,8°; Li—P—Li 132,1°) und zu nur zwei Sauerstoffatomen (Li—O 203,9 und 206,8; O … O 270,7 pm; O—Li—O 82,5°) des a priori dreizähnigen 2,5,8-Trioxanonan-Liganden ebenso wie Phosphor die Koordinationszahl 4 auf. Der P—C-Abstand ist mit 187,4 pm gegenüber dem Standard (185 pm) geringfügig verlängert. Vor einigen Jahren veröffentlichte Strukturen [26, 27] von (2,5,8-Trioxanonan-O2,O5,O8)- lithium-1-(phenylsulfonyl)alkyl-Verbindungen ermöglichen einen Vergleich charakteristischer Molekülparameter im zwei-oder dreifach koordinierenden Chelatliganden.
    Additional Material: 4 Ill.
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  • 2
    ISSN: 0044-2313
    Keywords: Bis[1,2-bis(dimethylamino)ethane-N,N′]lithium disilylphosphanide ; [Li(tmeda)2]+ cation(1) ; [(H3Si)2P]- anion ; X-ray structure determination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Derivatives of Molecular Compounds. VII. Bis[1,2-bis(dimethylamino)ethane-N,N′]lithium Disilylphosphanide  -  Synthesis and StructureCrystalline lithium phosphanides studied so far show a remarkably high diversity of structure types dependent on the ligands at lithium and the substituents at phosphorus. Bis[1,2-bis(dimethylamino)ethane-N,N′]lithium disilylphosphanide (1) discussed here, belongs to the up to now small group of compounds which are ionic in the solid state. It is best prepared from silylphosphane by twofold lithiation with lithium dimethylphosphanide first and subsequent monosilylation with silyl trifluoromethanesulfonate, followed by complexation. As found by X-ray structure determination (wR = 0.038) on crystals obtained from diethyl ether {monoclinic; space group P21/c; a = 897.8(1); b = 1 673.6(2); c = 1 466.8(1) pm; β = 90.73(1)° at -100 ± 3°C; Z = 4 formula units}, the lithium cation is tetrahedrally coordinated by four nitrogen atoms of two 1,2-bis(dimethylamino)ethane molecules. Characteristic parameters of the disilylphosphanide anion are a shortened average P—Si bond length of 217 pm (standard value 225 pm) and a Si—P—Si angle of 92.3°.
    Notes: Untersuchungen an kristallinen Lithiumphosphaniden ergeben in Abhängigkeit von den Liganden am Lithium- und den Substituenten am Phosphoratom eine überraschend große Strukturviefalt. Das aus Silylphosphan durch zweifache Lithinierung mit Lithium-dimethylphosphanid, nachfolgende einfache Silylierung mit Silyl-trifluormethansulfonat und anschließende Komplexierung gut zugängliche Bis[1,2-bis(dimethylamino)ethan-N,N′]lithium-disilylphosphanid (1) gehört zur bislang kleinen Gruppe der im Festkörper ionisch vorliegenden Verbindungen. Nach einer Röntgenstruktur-analyse (wR = 0,038) an den aus Diethylether isolierten Kristallen {monoklin; Raumgruppe P21/c; a = 897,8(1); b = 1 673,6(2); c = 1 466,8(1) pm; β = 90,73(1)° bei -100 ± 3°C; Z = 4 Formeleinheiten} ist Lithium verzerrt tetraedrisch von vier Stickstoffatomen aus zwei 1,2-Bis(dimethyl-amino)ethan-Molekülen umgeben. Das Disilylphosphanid-Anion weist einen gegenüber dem Standard von 225 auf 217 pm verkürzten mittleren P—Si-Abstand und einen Si—P—Si-Winkel von 92,3° auf.
    Additional Material: 3 Ill.
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