摘要:
The C-beta-H hydrogen in the diiron vinyliminium complexes [Fe-2{mu-eta(1):eta(3)-C-gamma(R')=C beta HC alpha= N(Me)(R)}(mu-CO)(CO)(Cp)(2)][SO3CF3] (R = Me, 1; R = Bz, 2 (Bz = CH2Ph); R = Xyl, 3 (Xyl =2,6-Me2C6H3)) is easily removed by sodium hydride; different products are consequently formed, depending on the nature of the substituents R and R'. Thus, deprotonation of [Fe-2{mu-eta(1):eta(3)-C(R')=CHC=N(Me)(R)}(mu-CO)(CO)(Cp)(2)] [SO3CF3] (R = Me, R' = COOMe, 1a; R = Me, R' = Me, 1b; R = Bz, R' = COOMe, 2a) yields the tetranuclear complexes [Fe-2{mu-eta(1):eta(2)-C(R')-CCN(Me)(R)}(mu-CO)(CO)(Cp)(2)](2) (R = Me, R'= COOMe, 4a; R = Me, R' = Me, 4b; R = Bz, R' = COOMe, 4c). Conversely, treatment with NaH of the vinyliminium complexes [Fe-2{mu-eta(1):eta(3)-C(R')=CHC=N(Me)(R)}(mu-CO)(CO)(Cp)(2)] [SO3CF3] (R = Me, R' = SiMe3, 1d; R = Me, R' = Tol, 1e; R = Bz, R' = SiMe3, 2b; R = Bz, R' = Tol, 2c (Tol = 4-MeC6H4); R = Xyl, R' = SiMe3, 3a; R = Xyl, R' = Tol, 3b; R = Xyl, R' = Ph, 3c) leads to the selective formation of the corresponding mu-aminocarbyne alkynyl complexes [Fe-2{mu-CN(Me)(R)}(mu-CO)(CO)(C CR')-(Cp)(2)] (R = Me, R' = SiMe3, 5a; R = Me, R' = Tol, 5b; R = Bz, R' = SiMe3, 5c; R = Bz, R' = Tol, 5d; R = Xyl, R' = SiMe3, 5e; R = Xyl, R' = Tol, 5f; R = Xyl, R' = Ph, 5g). Compounds 5c,d react with methyl iodide to give the vinyliminium cations [Fe-2{mu-eta(1):eta(3)-C(R')=C(Me)C= N(Me)(Bz)}(mu-CO)(CO)(Cp)(2)](+) (R'= SiMe3, 6a; R'= Tol, 6b). Finally, the reactions of [Fe-2{mu-eta(1):eta(3)-C(R')=CHC=N(Me)(R)}(mu-CO)(CO)(Cp)(2)] [SO3CF3] (R = Me, R' = Bu-n, 1c; R = Xyl, R' = Me, 3d; R = Xyl, R' = COOMe, 3e; R = Xyl, R' = CMe2OH, 3f) with NaH afford the 1-metalla-2-aminocyclopenta-1,3-dien-5-one species [Fe(Cp)(CO){CN(Me)(R)CHC(R')C(O)}] (R = Me, R' = Bu-n, 7a; R = Xyl, R' = Me, 7b; R = Xyl, R' = COOMe, 7c; R = Xyl, R' = CMe2OH, 7d). The molecular structures of 4a(.)CH(2)Cl(2), 4b, 5e, and 7b have been determined by X-ray diffraction studies.