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Issue 20, 2002
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The reactivity of diazabutadienes toward low oxidation state Group 13 iodides and the synthesis of a new gallium(I) carbene analogue

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Abstract

The reactions of two diazabutadiene ligands, Ar-DAB [(ArN[double bond, length as m-dash]CH)2 , Ar = 2,6-Pri2C6H3] and But-DAB [(ButN[double bond, length as m-dash]CH)2] with either GaI or an AlI3/Al mixture have afforded the paramagnetic compounds, [{IGaII(But-DAB)}2], [I2GaIII(But-DAB)] and [I2AlIII(Ar-DAB)] which have been characterised by X-ray crystallography and EPR spectroscopy. In addition, the diamagnetic, ionic complex, [I2AlIII(Ar-DAB)]I, has been prepared and structurally characterised. The reduction of [I2GaIII(Ar-DAB)] with potassium metal in the presence of various Lewis bases has led to three structurally characterised compounds, [{(Et2O)KGaI(Ar-DAB)}2], [{(TMEDA)KGaI(Ar-DAB)}2] and [:GaI(Ar-DAB)]2[{K(18-crown-6)}2(μ-18-crown-6)], which contain the second example of an anionic gallium(I) carbene analogue. In addition, the former two compounds display Ga⋯Ga interactions in the solid state which are unprecedented for this complex type.

Graphical abstract: The reactivity of diazabutadienes toward low oxidation state Group 13 iodides and the synthesis of a new gallium(i) carbene analogue

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Publication details

The article was received on 08 Jul 2002, accepted on 02 Sep 2002 and first published on 18 Sep 2002


Article type: Paper
DOI: 10.1039/B206605J
Citation: J. Chem. Soc., Dalton Trans., 2002,0, 3844-3850

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    The reactivity of diazabutadienes toward low oxidation state Group 13 iodides and the synthesis of a new gallium(I) carbene analogue

    R. J. Baker, R. D. Farley, C. Jones, M. Kloth and D. M. Murphy, J. Chem. Soc., Dalton Trans., 2002, 0, 3844
    DOI: 10.1039/B206605J

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