Heterotrinuclear Oxo-Bridged Fe(III)ORu(IV)OFe(III) Complexes of Ruthenium Porphyrin and Borylated Low-Spin Iron Dioximes(1). 1998

Isak Vernik, and Dennis V. Stynes
Department of Chemistry York University, North York, Ontario, Canada M3J 1P3.

The synthesis, structure, spectra, and reactivity of diamagnetic linear chain heterotrinuclear oxo-bridged complexes L-Fe(III) N(4)-O-Ru(IV)(TPP')-O-Fe(III)N(4)-L are described where TPP' is tetrakis(4-methoxyphenylporphyrinate), N(4) is one of the borylated bis(dioximate) macrocycles, N(4) = ((DMG)BF(2))(2) in 1, ((DMG)BPh(2))(2) in 2, and ((DPG)BF(2))(2) in 3, and L is a monodentate terminal ligand, L = BuNH(2), CH(3)CN, Py, 1-MeIm, (BuO)(3)P, etc. Crystal data for 3-(BuNH(2))(2) = [(BuNH(2))Fe((DPG)BF(2))(2)-O](2)Ru(TPP') monoclinic space group P2(1)/n, a = 16.845 Å, b = 27.184 Å, c = 24.593 Å, beta = 90.41 degrees, Fe-O = 1.79(1) Å, Ru-O = 1.80(1) Å, Fe-O-Ru = 175 degrees. Large porphyrin and phenyl ring current shifts permit ready characterization of the materials by (1)H NMR. A red-shifted Soret band at 433 nm and two charge transfer transitions in the 650-850 nm region are observed in the visible spectra. Clean reduction of 1, 2, and 3-(CH(3)CN)(2) with 4-tert-butylcatechol is observed giving Fe(II) and Ru(II) products. The kinetics of reduction parallel those of low-spin (&mgr;-oxo)diiron FeN(4) systems showing a 1/[CH(3)CN] dependence, but the rates are 10(3)-10(5) times slower. The Ru(IV) is proposed to stabilize the &mgr;-oxo-Fe bonds toward reductive cleavage via delocalization of the oxo pi electrons onto the ruthenium. Electrochemical data for the heterotrinuclear Fe-O-Ru-O-Fe systems are compared with those for the binuclear Fe-O-Fe systems. The HOMO is stabilized by 120 mV over the corresponding Fe-O-Fe system.

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