The current state of the chemistry of mono- and bidentate N-heterocyclic germylenes, stannylenes, plumbylenes, and related compounds is reviewed with special emphasis placed on benzannulated derivatives. The preparation, electronic structure, aggregation behaviour, and the coordination chemistry of the free benzannulated carbene analogues and their adducts with Lewis bases and complexes with transition metals are discussed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Mono‐ and Bidentate Benzannulated N‐Heterocyclic Germylenes, Stannylenes and Plumbylenes

Ungesättigte Moleküle mit Hauptgruppenmetallen

Synthetic applications of p block metal dimethylamido reagents

3 General Structural Aspects of Tin(II) Chemistry . . . . . . . . . . . . . 7 3.1 Compar ison between Structures of Sn(II) and Sn(IV) Compounds . . . 7 3.2 The Stereochemical Effect o f the Lone Electron Pair at Tin(II) . . . . 8 3.2.1 Coordinat ion Polyhedra . . . . . . . . . . . . . . . . . . . 9 3.2.2 Correlat ion between Tin-Ligand Distances and Coordinat ion Numbers . . . . . . . . . . . . . . . . . . . 13

/pdf/structure-and-reactivity-of-monomeric-molecular-tin-ii-42d2suvyow.pdf

Structure and reactivity of monomeric, molecular Tin(II) compounds

Imide transfer properties of ((THF)MgNPh)6 (1) and the synthesis of the related species {(THF)MgN(1-naphthyl)}6·2.25THF (2), via the reaction of dibutylmagnesium with H2N(1-naphthyl), in a THF/hept...

Imide Transfer Properties and Reactions of the Magnesium Imide ((THF)MgNPh)(6): A Versatile Synthetic Reagent.

1,3-Di-tert-butyl-2,2-dimethyl-1,3,2,4λ2-diazasilastannetidin (1) wird bei 50°C in Benzol quantitativ durch tert-Butylamin gespalten. Als Aminolyseprodukte entstehen je nach Molverhaltnis von tert-Butylamin zu 1 neben N,N-Di-tert-butyl-Si,Si-dimethylsilazan (3) ein tricyclischer Kafig Me2Si(NCMe3)2Sn2(NCMe3) (4) oder ein seco-norcubanartiges Molekul Sn3 (NCMe3)4H2 (5). Letzteres last sich leicht in das volle “Cuban” Sn4(NCMe3)4 (6) umwandeln. Die Konstitutionen der Verbindungen konnen aus hochaufgelosten 1H-NMR- und Massenspektren bestimmt werden.



Cyclic Diazastannylenes, VI. Preparation and Properties of Tetrameric tert-Butyliminostannylene and Related Cages



1,3-Di-tert-butyl-2,2-dimethyl-1,3,2,4λ2-diazasilastannetidine (1) undergoes quantitative cleavage with tert-butylamine at 50°C in benzoic solution. According to the molar ratios of tert-butylamine and 1 the aminolysis products are the tricyclic cage Me2Si(NCMe3)2Sn2(NCMe3) (4) or the seco-norcubane-like molecule Sn3(NCMe3)4H2 (5) plus N,N′-di-tert-butyl-Si,Si-dimethylsilazane (3). 5 can be converted to the complete “cubane” Sn4(NCMe3)4 (6) quite easily. The structures of the compounds can be determined from high resolution 1H NMR and mass spectral data.

/pdf/cyclische-diazastannylene-vi-darstellung-und-1248obv6my.pdf

Cyclische Diazastannylene, VI. Darstellung und Charakterisierung des tetrameren tert-Butyl-iminostannylens und verwandter Käfige

Die Kafigverbindung 1,5-Di-tert-butyl-6,6-dimethyl-3-oxa-1,5-diazonia-6-sila-2lambda2,4lambda2-distannatotricyclo[2.2.0.02,5]hexan (5) entsteht als SnCl2-Addukt bei vorsichtiger Hydrolyse eines Gemisches aus 1,3-Di-tert-butyl-2,2-dimethyl-1,3,2,4lambda2-diazasilastannetidin (1) und 1,3-Di-tert-butyl-4,4-dichlor-2,2-dimethyl-1,3,2,4lambda4-diazasilastannetidin (2). Die Kristalldaten sowie die Molekulstruktur wurden mit rontgenographischen Methoden erhalten (Tab. 1; R = 0.035). Die Struktur baut sich aus einem SnCl2-Band auf, an das die Kafigmolekule uber den Sauerstoff als Elektronendonor gebunden sind (Sn—O: 2.07 A). Der Kafig kann als N2Sn2-Tetraeder beschrieben werden (Sn—N: 2.31 A), dessen gegenuberliegende N—N- und Sn—Sn-Kanten jeweils mit Dimethylsilyl (Si-N: 1.76 A) bzw. Sauerstoff (Sn—O: 2.09 A) uberbruckt sind. Eine alternative Beschreibung ware ein Sechsring in der "twist"-Konformation D, der in 1,4- und 2,5-Position nochmals verbunden ist. Alle in der Struktur vorkommenden Zinnatome erreichen eine Stannat(II)-Geometrie.

/pdf/cyclische-diazastannylene-v-synthese-und-struktur-einer-2uows0csfr.pdf

Cyclische Diazastannylene, V. Synthese und Struktur einer neuartigen Käfigverbindung mit einem SiN2Sn2O‐Gerüst

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Cyclische Diazastannylene, VI. Darstellung und Charakterisierung des tetrameren tert-Butyl-iminostannylens und verwandter Käfige

Cyclische Diazastannylene, V. Synthese und Struktur einer neuartigen Käfigverbindung mit einem SiN2Sn2O‐Gerüst