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Novel bi- and trinuclear gallium halides and hydrides with acyclic and bicyclic guanidinate substituents: synthesis and reactivity

We report on the synthesis and characterization of new molecular Ga halides and hydrides with acyclic guanidinate substituents with bicyclic guanidinate substituents. Acyclic guanidinates were found to adopt terminal bonding modes like in the dimeric GaII compound [(iPr2N)C(NiPr)2GaI]2. In contrast,...

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Bibliographic Details
Main Authors: Rudolf, Daniel Thomas (Author) , Kaifer, Elisabeth (Author) , Himmel, Hans-Jörg (Author)
Format: Article (Journal)
Language:English
Published: 27 August 2010
In: European journal of inorganic chemistry
Year: 2010, Issue: 31, Pages: 4952-4961
ISSN:1099-0682
DOI:10.1002/ejic.201000598
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/ejic.201000598
Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.201000598
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Author Notes:Daniel Rudolf, Elisabeth Kaifer and Hans-Jörg Himmel
Description
Summary:We report on the synthesis and characterization of new molecular Ga halides and hydrides with acyclic guanidinate substituents with bicyclic guanidinate substituents. Acyclic guanidinates were found to adopt terminal bonding modes like in the dimeric GaII compound [(iPr2N)C(NiPr)2GaI]2. In contrast, bicyclic guanidinates prefer bridging bonding modes. Hence, the reaction between Me3N·GaH3 and htbo (1,4,6-triazabicyclo[3.3.0]oct-4-ene) affords the binuclear GaIII hydride [H2Ga(μ-tbo)]2. This new hydride turned out to be unstable in solution at 25 °C, dihydrogen is slowly eliminated. In the solid state, however, the hydride is stable up to 80 °C. The thermodynamic properties of this and similar dehydrogenation reactions were studied my means of quantum chemical calculations. With Ga2H5(μ3-O)(μ-tbn)2 and Ga2H5(μ3-O)(μ-hpp)2, two new hydrides were synthesized which can be regarded as the first hydrolysis intermediates of binuclear Ga hydrides with bridging guanidinate substituents.
Item Description:Gesehen am 22.06.2023
Physical Description:Online Resource
ISSN:1099-0682
DOI:10.1002/ejic.201000598

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