[<i>trans</i>-Bis(en)dioxoosmium(VI)]<i>trans</i>-bis(en)dioxoosmium(VI)[aqua-η<sup>1</sup>-sulfato-η<sup>2</sup>-sulfatoiron(II)][diaquabis(η<sup>1</sup>-sulfato)iron(II)] hexahydrate
作者:R. K. Murmann、C. L. Barnes
DOI:10.1107/s0108270199010070
日期:1999.12.15
Aqueous ferrous ion reacts reversibly with trans-[Os(en)(2)O-2](2+) producing an intensely blue complex ion which, in the presence of sulfate ion, produces the title complex, [OsO2(C2H8N2)(2)](2)[Os2Fe4O4(SO4)(8)(C2H8N2)(4)(H2O)(6)]. 12H(2)O, from H2O/CH3OH solution. The X-ray structure shows the unit cell to contain two discrete [Os(en)(2)O-2](2+) ions and two counter-ions having the basic linear core [(SO4)(2)-Fe-O-Os(en)(2)-O-Fe-(SO4)(2)](2-). Using sulfate ions as bridges, the latter ions form an infinite one-dimensional planar ribbon-like array separated by cations. In this array, the osmyl bond is lengthened [average 1.845(7) Angstrom] with respect to that of the parent ion [average 1.734(7) Angstrom], while the Fe-O bond is shortened to an average of 1.800(6) Angstrom with respect to the usual single-bend distance of 2.05 Angstrom. Sulfate ions serve as bridges between linear cores and are also chelated to a single ferrous ion. The strength of the bonds in the linear Fe-O-Os-O-Fe core as judged by bond-length changes suggests extensive electron delocalization between the metal centers.