A Nitrido-bridged Heterometallic Ruthenium(IV)/Iron(IV) Phthalocyanine Complex Supported by A Tripodal Oxygen Ligand, [Co(η5-C5H5){P(O)(OEt)2}3]−: Synthesis, Structure, and Its Oxidation to Give Phthalocyanine Cation Radical and Hydroxyphthalocyanine Complexes

Dinuclear iron nitrido phthalocyanine complexes are of interest owing to their applications in catalytic oxidation of hydrocarbons. While nitrido-bridged diiron phthalocyanine complexes are well documented, the oxidation chemistry of heterodinuclear iron(IV) phthalocyanine nitrides has not been well explored. In this paper we report on the synthesis of a heterometallic FeIV/RuIV phthalocyanine nitride and its oxidation to yield phthalocyanine cation radical and hydroxyphthalocyanine complexes. Treatment of [FeII(Pc)] (Pc2– = phthalocyanine dianion) with [RuVI(LOEt)(N)Cl2] (LOEt– = [Co(η5-C5H5){P(O)(OEt)2}3]−) (1) afforded the heterometallic μ-nitrido complex [Cl2(LOEt)RuIV(μ-N)FeIV(Pc)(H2O)] (2) that contains an RuIV=N = FeIV linkage with the Ru–N and Fe–N distances of 1.689(6) and 1.677(6) A, respectively, and Ru–N–Fe angle of 176.0(4)°. Substitution of 2 with 4-tert-butylpyridine (Bupy) gave [Cl2(LOEt)RuIV(μ-N)FeIV(Pc)(Bupy)]. The cyclic voltammogram of 2 displayed a reversible Pc-centered oxidation cou...