Abstract
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, [OsO 2 (C 2 H 8 N 2 ) 2 ] 2 [Os 2 Fe 4 O 4 (SO 4 ) 8 (C 2 H 8 N 2 ) 4 (H 2 O) 6 ].12H 2 O, from H 2 O/CH 3 OH 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 [(SO 4 ) 2 -Fe-O-Os(en) 2 -O-Fe-(SO 4 ) 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) A] with respect to that of the parent ion [average 1.734 (7) A], while the Fe-O bond is shortened to an average of 1.800 (6) A with respect to the usual single-bond distance of 2.05 A. 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.
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