Transition Metal Stannyl Complexes. 11.<sup>1</sup> Chelated ((Phosphinoalkyl)stannyl)iron Complexes by Intramolecular Oxidative Addition of Tin−Phenyl or Tin−Methyl Groups
作者:Ulrich Schubert、Stefanie Grubert
DOI:10.1021/om960424v
日期:1996.10.29
Reaction of Fe-2(CO)(9) with Ph(2)P(CH2)(n)SnR(2)R' (n = 2, R' = Ph, SnR(2) = SnPh(2) = SnPhMe, R' = Me, SnR(2) = SnMe(2); n = 1, 3, SnR(2)R' = SnPh(3)) results in the formation of(CO)(5-x)Fe[PPh(2)(CH2)(n)SnR(2)R'](x) (x = 1, 2). Upon UV irradiation, the chelated (phosphinoalkyl)-stannyl complexes (CO)(3)(R')FePPh(2)(CH2)(n)SnR(2) are obtained by intramolecular oxidative addition of the Sn-R' group. The complexes mer-(CO)(3)(H)(R'Si-3)FePPh(2)(CH2)(3)SnPh(3) (SiR'(3) = SiMePh(2), Si(OMe)(3)) are formed at -50 degrees C from (CO)(4)Fe(H)SiR'(3) and Ph(2)P(CH2)(2)SnPh(3). While the SiMePh(2) derivative is converted to the chelated complex (CO)(3)(Ph)FePPh(2)-(CH2)(2)SnPh(2) by HSiMePh(2) elimination upon heating, the Si(OMe)(3) derivative does not give the intramolecular oxidative addition. Photochemical reaction of (CO)(3)(Ph)FePPh(2)-(CH2)(2)SnPh(2) with Ph(2)P(CH2)(2)SnPh(3) gives the substitution product (CO)(2)(Ph)Fe[PPh(2)-(CH2)(2)SnPh(2)]PPh(2)(CH2)(2)SnPh(3). While a second oxidative addition to the iron center by the dangling SnPh(3) group is not possible, the Sn-Ph group readily adds to a (Ph(3)P)(2)Pt fragment to give (CO)(2)(Ph)Fe[PPh(2)(CH2)(2)SnPh(2)]PPh(2)(CH2)(2)SnPh(2)Pt(Ph)(PPh(3))(2). The related complex (CO)(3)(H)[(MeO)(3)Si]FePPh(2)(CH2)(2)SnPh(2)Pt(Ph)(PPh(3))(2) is similarly obtained from (CO)(3)(H)[(MeO)(3)-Si]FePPh(2)(CH2)(2)SnPh(3).