Mono‐ and Binuclear Ruthenium Corroles: Synthesis, Spectroscopy, Electrochemistry, and Structural Characterization

Abstract

The aim of this research was to prepare mononuclear ruthenium corroles, because of the well-documented potency of analogous porphyrin complexes in catalysis. The syntheses of the mononuclear nitrosyl complexes [Ru(tpfc)(NO)] and [Ru(tdcc)(NO)] (tpfc=trianion of 5,10,15-tris(pentafluorophenyl)corrole, tdcc=trianion of 5,10,15-tris(2,6-dichlorophenyl)corrole), and of the binuclear [[Ru(tpfc)](2)] were achieved by using [[Ru(cod)Cl(2)](x)] (cod=cyclooctadiene) as the metal source. The NMR spectra of all three complexes clearly demonstrate that they are diamagnetic; this is consistent with a triple bond between the metal ions in [[Ru(tpfc)](2)] and is expected for classical [MNO](6) complexes. These features were further substantiated by the stretching frequencies of the [MNO] moieties, electrochemical measurements on all complexes, and the X-ray crystal structures of [Ru(tpfc)(NO)] and [[Ru(tpfc)](2)]. A comparison of the spectroscopic and structural characteristics of these new complexes with analogous iron corroles, as well as with iron and ruthenium porphyrins, suggests that it will be hard to obtain mononuclear ruthenium corroles without pi-accepting ligands.

Relativistic Effects on a Metal–Metal Bond: Osmium Corrole Dimers

“…sensitive Soret maximum. 41 By this criterion, the Ru and Os corrole dimers, like the majority of 4d and 5d metallocorroles (including MoO, 42 RuN, 14 OsN, 16 TcO, 43 ReO, 44 Pt, 45 and Au 46,47,48,49 corroles), appear to be innocent. The spectra of both series of dimers are nonetheless unusual, relative to first-row transition metal corroles, and are characterized by intense near-UV features.…”

Electronic Structures and Reactivities of Corrole−Copper Complexes

“…This single corrole and its variants have been shown to support a large variety of metal ions (Cr,7 Mn,8 Fe,9 Ru,10 Co,9,11 Rh,9,12 Ni,13 Pd,12 Cu,12 Zn,14 Al,15 Ga,16 Ge,9b Sn,9b P9b) and many of these complexes have been fully characterized in several oxidation and coordination states. The novel features that were found for 1 and its metal complexes include very high fluorescence quantum yields,13,14 easily achieved chirality,10,12 potent catalytic activity,17 facile methodologies for further functionalization,18 and selective interactions with tumor cells 19. Another important development is the introduction of corroles with meso ‐aryl groups that contain large ortho ‐phenyl substituents (Cl, CH 3 ), whose impact in affecting catalysis was demonstrated recently 20…”

Synthesis, characterization and solvent/structural effects on spectral and redox properties of cobalt triphenylcorroles in nonaqueous media

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Corroles and metallocorroles have attracted a great deal of interest in recent years [1][2][3][4][5][6][7][8], in part because of improved synthetic methods which make them more readily available than in the past [1,2,6,7] and in part because these compounds have potential applications as catalysts for a variety of reactions [4,[9][10][11][12][13][14][15][16][17][18][19][20][21][22]. One of the most frequently studied groups of metallocorroles are the cobalt derivatives which have been characterized as to their spectral and electrochemical properties under many different solution conditions [1,2,6,[23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39]

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