Organometallic Reactions of Ruthenium and Osmium Porphyrins

Alkyl and aryl systems - As already mentioned in Sect. 3.2, dialkyl ruthenium and osmium porphyrins have been synthesized according to Eq. (22) by the reaction of metalloporphyrin dianions [M(P)]2 with alkyl iodides [223, 260, 261,307]. These dianions have been obtained by reduction of porphyrin dimers [M(P)]2. 

The resulting dialkylmetal(IV) derivatives are thought to be diamagnetic. The diethylruthenium complex Ru(C2Hs)2(P) was thermally labile at room temperature, and a mixture of the ethylidene species Ru(CHCH3) (P) and the Ru(III) compound RuC2H5(P) was formed via independent radical processes [307] (Eq. 23). 

Some diarylruthenium(IV) species were made from RuBr2(TPP) or RuBr2(OEP) with LiPh [157, 251] (Eq. 24). 

Thermolysis of RuPh2(TPP) at 100 °C for 30 h in benzene produces a phenyl-ruthenium(III) complex, RuPh(TPP) [155] (see Table 2). In contrast to RuPh2(P) and FePh(P) [222] no N-arylation occurred on oxidation of the five-coordinate RuPh(P) [306]. 

Reduction of RuMe2(OEP) with sodium naphthalenide, NaNp, led to decomposition of the anion thus formed (sequence 25) [308]. 

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