Abstract
The NHC alane and gallane adducts (NHC)·AlH2I (NHC = Me2ImMe 7, iPr2Im 8, iPr2ImMe 9) and (NHC)·GaH2I (NHC = Me2ImMe 10, iPr2ImMe 11, Dipp2Im 12; R2Im = 1,3‐di‐organyl‐imidazolin‐2‐ylidene; Dipp = 2,6‐diisopropylphenyl; iPr = isopropyl; Me2ImMe = 1,3,4,5‐tetra‐methyl‐imidazolin‐2‐ylidene) were prepared either by the simple yet efficient reaction of the NHC adduct (NHC)·AlH3 with elemental iodine or by the treatment of (NHC)·GaH3 with an excess of methyl iodide at room temperature. The reaction of one equivalent of the group 13 NHC complexes with an additional equivalent of the corresponding NHC afforded cationic aluminium and gallium hydrides [(NHC)2·AlH2]+I− (NHC = Me2ImMe 13, iPr2Im 14, iPr2ImMe 15) and [(NHC)2·GaH2]+I− (NHC = Me2ImMe 16, iPr2ImMe 17) and the normal and abnormal NHC coordinated compound [(Dipp2Im)·GaH2(aDipp2Im)]+I− 18. Compounds 7–18 were isolated and characterized by means of elemental analysis, IR and multinuclear NMR spectroscopy and by X‐ray diffraction of the compounds 7, 9, 10, 15, 16 and 18.
Highlights
Aluminum and gallium hydrides are important reagents in organic and inorganic synthesis, e.g. for reductions and hydride transfer,[1,2] as well as important materials, in particular for hydride storage.[3]
13 N-heterocyclic carbenes (NHCs) complexes with an additional equivalent of the corresponding NHC afforded cationic aluminium and gallium hydrides [(NHC)2·AlH2]+I− (NHC = Me2ImMe 13, iPr2Im 14, iPr2ImMe 15) and [(NHC)2·GaH2]+I− (NHC = Me2ImMe 16, iPr2ImMe 17) and the normal and abnormal NHC coordinated compound [(Dipp2Im)·GaH2(aDipp2Im)]+I− 18
The coordination of NHCs, for example, to alanes and gallanes leads to the synthesis of stable NHC metal hydride adducts.[7,11,12]
Summary
Aluminum and gallium hydrides are important reagents in organic and inorganic synthesis, e.g. for reductions and hydride transfer,[1,2] as well as important materials, in particular for hydride storage.[3]. 13 NHC complexes with an additional equivalent of the corresponding NHC afforded cationic aluminium and gallium hydrides [(NHC)2·AlH2]+I− (NHC = Me2ImMe 13, iPr2Im 14, iPr2ImMe 15) and [(NHC)2·GaH2]+I− (NHC = Me2ImMe 16, iPr2ImMe 17) and the normal and abnormal NHC coordinated compound [(Dipp2Im)·GaH2(aDipp2Im)]+I− 18. We reacted the compounds (NHC)·AlH3 (NHC = Me2ImMe 1, iPr2Im 2, iPr2ImMe 3) with 0.5 equivalents of elemental iodine I2 in toluene at room temperature.
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