Synthesis and Characterization of Pentaphosphino Zero-Valent Iron Complexes and Their Corresponding Iron(II)-Chloride and -Hydride Complexes

A pentaphosphino iron(II)-chloride species [(t)SiP(3)(dmpm)FeCl][Cl] (1-Cl) ((t)SiP(3) = (t)BuSi(CH(2)PMe(2))(3), dmpm = Me(2)PCH(2)PMe(2)) was prepared from [((t)SiP(3)Fe)(2)(mu-Cl)(3)][Cl] and dmpm. This species was reduced to give the corresponding iron(0) complex, (t)SiP(3)(dmpm)Fe (3), in near quantitative yield. Analogous complexes [SiP(3)(dmpe)FeCl][Cl] (2-Cl) and SiP(3)(dmpe)Fe (4) (SiP(3) = MeSi(CH(2)PMe(2))(3), dmpe = Me(2)PCH(2)CH(2)PMe(2)) were prepared in the same manner as 1 and 3 but with lower yields because of competitive ligand rearrangement reactions that gave byproduct of trans-(dmpe)(2)FeCl(2) and (dmpe)(5)Fe(2) (5). [(t)SiP(3)(dmpm)FeH][A] (6) was prepared from the reaction of 3 with weak acids (HA), and the pK(a) of 6 was established to be approximately 25. Attempts to prepare pentaphosphino-iron(0) complexes of the form SiP(3)(PR(3))(2)Fe using PPh(3) and PMe(3) resulted in cyclometalated products, SiP(3)FeH((o-C(6)H(4))PPh(2)) (7) and SiP(3)FeH(CH(2)PMe(2)) (8). Synthesis and characterization of these complexes, including crystal structures of 1-5, are reported.