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  • 1
    ISSN: 0044-2313
    Keywords: Magnesium Compounds ; Phosphoraneiminato Complexes ; Crystal Structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Phosphaneimine and Phosphoraneiminato Complexes of Magnesium. The Crystal Structures of [MgBr1,25I0,75(Me3SiNPMe3)(OEt2)], [MgI2(Me3SiNPMe3)2], [Mg2I2(Me3SiNPMe2CH2)(Me3SiNPMe2CH2CH(Me)O)(OEt2)], and [MgBr(NPMe3)]4 · C7H8By reactions of the silylated phosphaneimine Me3SiNPMe3 with the Grignard reagents EtMgBr and MeMgI, respectively, the carbanionic phosphoraneiminato derivatives [XMg(CH2PMe2NSiMe3)]n (X = Br, I) can be isolated as main products. The by-products of these reactions, [MgBr1.25I0.75(Me3SiNPMe3)(OEt2)], [MgI2(Me3SiNPMe3)2] and [Mg2I2(CH2PMe2NSiMe3)(O(Me)CHCH2PMe2NSiMe3)(OEt2)] were identified by crystal structure determinations. The phosphoraneiminato complex [MgBr(NPMe3)]4 · C7H8 with hetero cubane structure is formed by a metathesis reaction of [ZnBr(NPMe3)]4 with RMgBr (R = Ph. Mes).
    Notes: Als Hauptprodukte der Umsetzungen des silylierten Phosphanimins Me3SiNPMe3 mit den Grignard-Reagentien EtMgBr und MeMgl wurden die carbanionischen Phosphaniminato-Derivate [XMg(CH2Pme2NSiMe3)]n (X = Br, I) isoliert. Als Nebenprodukte wurden [MgBr1,25I0,75(Me3SiNPMe3)(OEt2)], [Mgl2(Me3SiNPMe3)2] und [Mg2I2(CH2PMe2NSiMe3)(O(Me)CHCH2PMe2NSiMe3(OEt2)] durch röntgenographische Strukturanalysen identifiziert. Den Phosphaniminato-Komplex [MgBr(NPMe3)]4 · C7H8 mit Heterocuban-Struktur erhielten wir durch Metathese-Reaktion aus [ZnBr(NPMe3)]4 und RMgBr (R = Ph, Mes).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 351-356 
    ISSN: 0044-2313
    Keywords: Organomanganese Compounds ; Phosphoraneiminato Complexes ; Syntheses ; Crystal Structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organomanganese Phosphoraneiminato Complexes with Heterocubane StructureThe organomanganese phosphoraneiminato complexes [MnR(NPEt3)]4 (R = Me, C=C—Ph, C=C—Tol, C=C—CMe3, C=C—SiMe3) with heterocubane structures have been prepared by reaction of the bromo derivative [MnBr(NPEt3)]4 with the corresponding lithium reagents LiR in THF/hexane solution, forming shiny red, very reactive compounds which are well soluble in hydrocarbons. They were characterized by mass spectroscopy, IR spectroscopy and by crystal structure determinations. According to these the compounds form nearly perfect Mn4N4 heterocubane frameworks with m̈3-N bridges of the phosphoraneiminato groups with Mn—N bond lengths of 214.5 pm in average which leads to Mn … Mn contacts of 299.5 pm in average. The organic residues R are terminal bonded with Mn—C distances Mn—Me of 219.5 pm and Mn—C=C—R of 207.6 pm in average.
    Notes: Die organisch substituierten Phosphanimi nato-Komplexe des Mangan(II) mit Heterocubanstruktur [MnR(NPEt3)]4 (R = Me, C=C—Ph, C=C—Tol, C=C—CMe3, C=C—SiMe3) werden durch Reaktion des Bromoderivates [MnBr(NPEt3)]4 mit den entsprechenden Lithium-Reagentien LiR in THF/Hexan als leuchtend rote, sehr reaktive, in Kohlenwasserstoffen leicht lösliche Verbindungen erhalten. Sie werden durch die Massen- und IR-Spektren sowie durch Kristallstrukturanalysen charakterisiert. Danach werden je vier Manganatome über je vier m̈3-N-Atome der Phosphan-iminato-Gruppen zu nur wenig verzerrten m̈3-N4-Kuben mit Mn—N-Abständen von im Mittel 214,5 pm verbrückt, was zu Mn … Mn-Kontakten von 299,5 pm führt. Die Reste R sind terminal gebunden mit Mn—C-Abständen Mn—Me von 219,5 pm und Mn—C=C—R von im Mittel 207,6 pm.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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