Heterobimetallic nitrido porphyrin complexes with the [(L)(por)M-N-M'(L)Cl] formula {por = 5,10,15,20-tetraphenylporphyrin (TPP) or 5,10,15,20-tetra(p-tolyl)porphyrin (TTP) dianion; L = [Co(η-CH){P(O)(OEt)}]; M = Fe, Ru, or Os; M' = Ru or Os; L = HO or pyridine} have been synthesized, and their electrochemistry has been studied. Treatment of trans-[Fe(TPP)(py)] (py = pyridine) with Ru(VI) nitride [Ru(L)(N)Cl] (1) afforded Fe/Ru μ-nitrido complex [(py)(TPP)Fe(μ-N)Ru(L)Cl] (2). Similarly, Fe/Os analogue [(py)(TPP)Fe(μ-N)Os(L)Cl] (3) was obtained from trans-[Fe(TPP)(py)] and [Os(L)(N)Cl]. However, no reaction was found between trans-[Fe(TPP)(py)] and [Re(L)(N)Cl(PPh)]. Treatment of trans-[M(TPP)(CO)(EtOH)] with 1 afforded μ-nitrido complexes [(HO)(TPP)M(μ-N)Ru(L)Cl] [M = Ru (4a) or Os (5)]. TTP analogue [(HO)(TTP)Ru(μ-N)Ru(L)Cl] (4b) was prepared similarly from trans-[Ru(TTP)(CO)(EtOH)] and 1. Reaction of [(HO)(por)M(μ-N)M(L)Cl] with pyridine gave adducts [(py)(por)M(μ-N)Ru(L)Cl] [por = TTP, and M = Ru (6); por = TPP, and M = Os (7)]. The diamagnetism and short (por)M-N(nitride) distances in 2 [Fe-N, 1.683(3) Å] and 4b [Ru-N, 1.743(3) Å] are indicative of the M═N═M' bonding description. The cyclic voltammograms of the Fe/Ru (2) and Ru/Ru (4b) complexes in CHCl displayed oxidation couples at approximately +0.29 and +0.35 V versus Fc (Fc = ferrocene) that are tentatively ascribed to the oxidation of the {LRu} and {Ru(TTP)} moieties, respectively, whereas the Fe/Os (3) and Os/Ru (5) complexes exhibited Os-centered oxidation at approximately -0.06 and +0.05 V versus Fc, respectively. The crystal structures of 2 and 4b have been determined.

Treatment of Ru(dCHPh)Cl 2 (PCy 3 ) 2 (Cy = cyclohexyl) with K[N(i-Pr 2 PS) 2 ] afforded a mixture of Ru-(dCHPh)[N(i-Pr 2 PS) 2 ](PCy 3 )Cl (1) and Ru(dCHPh)-[N(i-Pr 2 PS) 2 ] 2 (2). Reaction of 1 with TlOPh gave Ru-(dCHPh)[N(i-Pr 2 PS) 2 ](PCy 3 )(OPh) (3), whereas that with NaOMe yielded the Ru(II) hydride compound Ru(H) [N(i-Pr 2 PS) 2 ][PCy 2 (η 2 -C 6 H 9 )] ( 4), in which the dicyclohexyl(cyclohex-3-enyl)phosphine ligand binds to Ru via the phosphorus atom and the CdC bond of the cyclohex-3-enyl ring. The structures of complexes 3 and 4 have been established by X-ray crystallography.

Iridium porphyrin complexes containing μ-nitrido, hydroxo, hydrosulfido, and alkynyl ligands have been synthesized and structurally characterized, and their oxidation has been studied.