Reactions of Diazo Compounds at μ-Vinyliminium Ligands: Synthesis of Novel Dinuclear Azine−Bis(alkylidene) Complexes

摘要: The vinyliminium complexes [M2{μ-η1:η3-Cγ(R‘)CβHCαN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (1a−f) react with ethyl diazoacetate in the presence of NaH, affording azine−bis(alkylidene) [M2{μ-η1:η2-Cγ(R‘)Cβ{NNCδ(COOMe)H}CαN(Me)(R)}(μ-CO)(CO)(Cp)2] (M = Fe, R 2,6-Me2C6H3 (Xyl), R‘ Me (2a), p-C6H4Me (Tol) (2b), CO2Me (2c), Bun (2d); M (2e); Ru, Xyl, (2f)) 70÷77% yields. Analogous reactions N2CPh2 lead to formation [Fe2{μ-η1:η2-Cγ(R‘)Cβ(NNCδPh2)CαN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (R‘ (3a), COOMe (3b)). ligand easily undergoes electrophilic addition, cationic hydrazone−vinyliminium [Fe2{μ-η1:η3-Cγ(R‘)Cβ{N(E)NCδ(R‘ ‘)(R‘ ‘‘)}CαN(Me)(Xyl)}(μ-CO)(CO)(Cp)2]+ Me, R‘ ‘ CO2Et, R‘ ‘‘ E H, 4a; COOEt, 4b; Bun, 4c; Ph, 4d). Reactions 4b,d NaBH4 result addition hydride at Cα vinylim...