Monovalent group 13 diyls of the type LM(L=HC[C(Me)NAr]^(2);Ar=2,6-iPr_(2)C_(6)H_(3))are group 13 analogues of NHCs.While LAl is known to undergo(1,4)-cycloaddition with a variety of dienes including arenes,LGa only r...Monovalent group 13 diyls of the type LM(L=HC[C(Me)NAr]^(2);Ar=2,6-iPr_(2)C_(6)H_(3))are group 13 analogues of NHCs.While LAl is known to undergo(1,4)-cycloaddition with a variety of dienes including arenes,LGa only reacted with acyclic dienes,i.e.,butadiene and Danishefsky's diene,via(1,4)-cycloaddition to give LGa(C_(6)H_(10))(1)and LGa(C_(8)H_(16)O_(2)Si)(2),whereas LIn completely failed to react with these substrates.However,LGa and LIn both reacted with the electron-poor hexachlorobutadiene with oxidative addition of the allyl C-Cl bond to give L(Cl)M(C_(4)Cl_(5))(M=Ga 3;In 4).Similarly,L(X)MR(X=Cl,R=Bn,M=Ga 5,In 6;X=Br;R=Et,M=Ga 7,In 8)were obtained from oxidative addition with alkyl halides.Compounds 3-8 did not react with benzaldehyde,whereas the cation[LGaCH_(2)Ph]^(+)(10),obtained by reaction of L(Cl)GaBn with AgOTf and NaB(C_(6)F_(5))_(4),reacted rapidly,but no defined reaction product was identified.展开更多
文摘Monovalent group 13 diyls of the type LM(L=HC[C(Me)NAr]^(2);Ar=2,6-iPr_(2)C_(6)H_(3))are group 13 analogues of NHCs.While LAl is known to undergo(1,4)-cycloaddition with a variety of dienes including arenes,LGa only reacted with acyclic dienes,i.e.,butadiene and Danishefsky's diene,via(1,4)-cycloaddition to give LGa(C_(6)H_(10))(1)and LGa(C_(8)H_(16)O_(2)Si)(2),whereas LIn completely failed to react with these substrates.However,LGa and LIn both reacted with the electron-poor hexachlorobutadiene with oxidative addition of the allyl C-Cl bond to give L(Cl)M(C_(4)Cl_(5))(M=Ga 3;In 4).Similarly,L(X)MR(X=Cl,R=Bn,M=Ga 5,In 6;X=Br;R=Et,M=Ga 7,In 8)were obtained from oxidative addition with alkyl halides.Compounds 3-8 did not react with benzaldehyde,whereas the cation[LGaCH_(2)Ph]^(+)(10),obtained by reaction of L(Cl)GaBn with AgOTf and NaB(C_(6)F_(5))_(4),reacted rapidly,but no defined reaction product was identified.
