The Lewis base-supported terminal uranium imido metallocene,[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U^(V)N(mesityl)(dmap)(2),is readily accessible from the reaction of[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)UMe_(2)(...The Lewis base-supported terminal uranium imido metallocene,[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U^(V)N(mesityl)(dmap)(2),is readily accessible from the reaction of[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)UMe_(2)(1)with mesitylNH_(2)in toluene in the presence of 4-dimethylaminopyridine(dmap).With compound 2 in hand,its reactivity towards small molecules was studied in detail.It reacts with terminal alkynes such as PhCuCH to form the amido alkynyl complex[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U[N(mesityl)CHvCHPh](CuCPh)(3)exclusively.In the reaction with thio-ketone Ph_(2)CS,CS_(2),isothiocyanate PhNCS and ketone Ph_(2)CO,the initial[2+2]cycloaddition intermediates are too labile to be isolated,yielding[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U(S_(2)CPh_(2))(dmap)(4)or dimeric sulfido and oxido complexes{[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U}_(2)(μ-E)_(2)(E=S(5),O(6)),respectively.Moreover,complex 2 may also behave as a nucleophile in the reaction with bis(catecholato)diboron(B_(2)cat_(2)),yielding the amido catecholate complex[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U[N(mesityl)B(BO_(2)C_(6)H_(4))O(C_(6)H_(4))O](8).In addition,the imido moiety of 2 may also engage in deprotonation reactions as demonstrated by its reactivity with the carboxamide PhCONH(p-tolyl)and organic nitrile PhCH_(2)CN,obtaining the uranium(IV)bis-amidate complex[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U[OC(Ph)N(p-tolyl)]_(2)(7)and the uranium(IV)iminato amido complex[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U[N(mesityl)vC(CH_(2)Ph)NH](NvCvCHPh)(9),respectively.Furthermore,2 may also participate in single-and two-electron transfer processes.It is singly oxidized by CuI,Ph_(2)S_(2),Ph_(2)Se_(2)and Ph_(3)CN_(3),yielding the uranium(V)imido complexes[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U^(V)N(mesityl)(X)(X=I(12),PhS(13),PhSe(14),and N_(3)(17)),or doubly oxidized by organic azides(RN_(3)),forming the uranium(VI)bis-imido metallocenes[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U^(V)N(mesityl)(vNR)(R=p-tolyl(15),mesityl(16)),respectively.Nevertheless,the addition of 1,2-diphenylhydrazine PhNHNHPh to complex 2 results in deprotonation and ligand elimination processes,yielding the uranium(V)bis-imido complex[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]U[vNPh]_(2)(dmap)_(3)(11)in the presence of dmap.展开更多
Addition of N-heterocyclic carbenes(L=1,3-di-tert-butylimidazol-2-ylidene(ItBu),1,3-di-iso-propyl-4,5-dimethylimidazol-2-yildene(IiPr_(2)Me_(2)),1,3-mesitylimidazol-2-yildene(IMes)and 1,3-di-(2,6-di-isopropylphenyl)im...Addition of N-heterocyclic carbenes(L=1,3-di-tert-butylimidazol-2-ylidene(ItBu),1,3-di-iso-propyl-4,5-dimethylimidazol-2-yildene(IiPr_(2)Me_(2)),1,3-mesitylimidazol-2-yildene(IMes)and 1,3-di-(2,6-di-isopropylphenyl)imidazol-2-yildene(IPr))to the iron half-sandwich complex[Cp’FeI]_(2)(Cp’=η^(5)-1,2,4-(Me_(3)C)_(3)C_(5)H_(2),1)forms the neutral,16VE adducts[Cp’FeI(L)](2–5)in moderate to excellent yields.These complexes were structurally characterised.展开更多
基金National Natural Science Foundation of China(grant no.22271017)Deutsche Forschungsgemeinschaft(DFG)through the Heisenberg program(WA 2513/8)。
文摘The Lewis base-supported terminal uranium imido metallocene,[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U^(V)N(mesityl)(dmap)(2),is readily accessible from the reaction of[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)UMe_(2)(1)with mesitylNH_(2)in toluene in the presence of 4-dimethylaminopyridine(dmap).With compound 2 in hand,its reactivity towards small molecules was studied in detail.It reacts with terminal alkynes such as PhCuCH to form the amido alkynyl complex[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U[N(mesityl)CHvCHPh](CuCPh)(3)exclusively.In the reaction with thio-ketone Ph_(2)CS,CS_(2),isothiocyanate PhNCS and ketone Ph_(2)CO,the initial[2+2]cycloaddition intermediates are too labile to be isolated,yielding[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U(S_(2)CPh_(2))(dmap)(4)or dimeric sulfido and oxido complexes{[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U}_(2)(μ-E)_(2)(E=S(5),O(6)),respectively.Moreover,complex 2 may also behave as a nucleophile in the reaction with bis(catecholato)diboron(B_(2)cat_(2)),yielding the amido catecholate complex[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U[N(mesityl)B(BO_(2)C_(6)H_(4))O(C_(6)H_(4))O](8).In addition,the imido moiety of 2 may also engage in deprotonation reactions as demonstrated by its reactivity with the carboxamide PhCONH(p-tolyl)and organic nitrile PhCH_(2)CN,obtaining the uranium(IV)bis-amidate complex[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U[OC(Ph)N(p-tolyl)]_(2)(7)and the uranium(IV)iminato amido complex[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U[N(mesityl)vC(CH_(2)Ph)NH](NvCvCHPh)(9),respectively.Furthermore,2 may also participate in single-and two-electron transfer processes.It is singly oxidized by CuI,Ph_(2)S_(2),Ph_(2)Se_(2)and Ph_(3)CN_(3),yielding the uranium(V)imido complexes[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U^(V)N(mesityl)(X)(X=I(12),PhS(13),PhSe(14),and N_(3)(17)),or doubly oxidized by organic azides(RN_(3)),forming the uranium(VI)bis-imido metallocenes[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]_(2)U^(V)N(mesityl)(vNR)(R=p-tolyl(15),mesityl(16)),respectively.Nevertheless,the addition of 1,2-diphenylhydrazine PhNHNHPh to complex 2 results in deprotonation and ligand elimination processes,yielding the uranium(V)bis-imido complex[η^(5)-1,3-(Me_(3)Si)_(2)C_(5)H_(3)]U[vNPh]_(2)(dmap)_(3)(11)in the presence of dmap.
基金the financial support by the Deutsche Forschungsgemeinschaft(DFG)through the Emmy-Noether and the Heisenberg program(WA 2513/2 and WA 2513/6,respectively)。
文摘Addition of N-heterocyclic carbenes(L=1,3-di-tert-butylimidazol-2-ylidene(ItBu),1,3-di-iso-propyl-4,5-dimethylimidazol-2-yildene(IiPr_(2)Me_(2)),1,3-mesitylimidazol-2-yildene(IMes)and 1,3-di-(2,6-di-isopropylphenyl)imidazol-2-yildene(IPr))to the iron half-sandwich complex[Cp’FeI]_(2)(Cp’=η^(5)-1,2,4-(Me_(3)C)_(3)C_(5)H_(2),1)forms the neutral,16VE adducts[Cp’FeI(L)](2–5)in moderate to excellent yields.These complexes were structurally characterised.
