Stepwise Deoxygenation of Nitrite as a Route to Two Families of Ruthenium Corroles: Group 8 Periodic Trends and Relativistic Effects

Abstract

Given the many applications of ruthenium porphyrins, the rarity of ruthenium corroles and the underdeveloped state of their chemistry are clearly indicative of an area ripe for significant breakthroughs. The tendency of ruthenium corroles to form unreactive metal–metal-bonded dimers has been recognized as a key impediment in this area. Herein, by exposing free-base meso-tris(p-X-phenyl)corroles, H₃[TpXPC] (X = CF₃, H, Me, and OMe), and [Ru(COD)Cl₂]x in refluxing 2-methoxyethanol to nitrite, we have been able to reliably intercept the series Ru[TpXPC](NO) in a matter of seconds to minutes and subsequently RuVI[TpXPC](N), the products of a second deoxygenation, over some 16 h. Two of the Ru^VIN complexes and one ruthenium corrole dimer could be crystallographically analyzed; the Ru–N_nitrido distance was found to be ∼1.61 Å, consistent with the triple-bonded character of the Ru^VIN units and essentially identical with the Os–N_nitrido distance in analogous osmium corroles. Spectroscopic and density functional theory (DFT) calculations suggest that the RuNO corroles are best viewed as innocent {RuNO}6 complexes, whereas the analogous FeNO corroles are noninnocent, i.e., best viewed as {FeNO}7-corrole^•2–. Both RuVIN and Os^VIN corroles exhibit sharp Soret bands, suggestive of an innocent macrocycle. A key difference between the two metals is that the Soret maxima of the Os^VIN corroles are red-shifted some 25 nm relative to those of the Ru^VIN complexes. Careful time-dependent DFT studies indicate that this difference is largely attributable to relativistic effects in Os^VIN corroles. The availability of two new classes of mononuclear ruthenium corroles potentially opens the door to new applications, in such areas as catalysis and cancer therapy.