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The synthesis and characterization of (NHC)·GaH2(cAACMeH) (NHC = Me2ImMe5, iPr2ImMe6 and Dipp2Im 7), the products of an oxidative addition of (NHC)·GaH3 to cAACMe, are presented. The adduct (Dipp2ImH)·GaH34 reacts with two equivalents of cAACMe under the release of Dipp2ImH and insertion of two cAACMe molecules into the Ga-H bond to give the bisalkylgallane (cAACMeH)2GaH 8. If one or two hydrogen atoms of the NHC gallane adducts are replaced with an electron-withdrawing chloride substituent, a selective insertion of cAACMe into the Ga-H

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