[1,4]-Cycloaddition and C–X Bond Activation Reactions of monovalent Group 13 diyls

Abstract

Monovalent group 13 diyls LM (M = Ga, In; L = HC[C(Me)NAr]2; Ar = 2,6-iPr2C6H3) react with acyclic dienes with [1,4]-cycloaddition to five-membered metallaheterocycles or with oxidative addition of the C-X bond as is also observed with alkyl and aryl halides. While only LGa reacted with butadiene and Danishefsky’s diene to LGa(C6H10) (1) and LGa(C8H16O2Si) (2), both LGa and LIn reacted with electron poor hexachlorobutadiene selectively with oxidative addition of the allyl C–Cl bond to L(Cl)M(C4Cl5) (Ga 3; In 4), Analogously, both group 13 diyls reacted with BzCl (Bz = benzyl) and EtBr with oxidative addition of the C-X bond to L(X)MR (X = Cl, R = Bz, M = Ga 5, In 6; X = Br; R = Et, M = Ga 7, In 8). We furthermore report the synthesis of the cation [LGaCH2Ph]+ (10+) by reaction of L(TfO)Ga(CH2C6H5) (9) with NaB(C6F5)4).