Electronic Structures and Reactivities of Corrole−Copper Complexes

Abstract

The spectroscopic and electrochemical examination of the mononuclear copper complexes of 5,10,15-tris(pentafluorophenyl)corrole and 5,10,15-tris(2,6-dichlorophenyl)corrole (1a and 2a, respectively) and of the corresponding dinuclear corrole dimers 1b and 2b reveal the existence of two almost degenerate electronic states. The lower state consists of copper(III) ions coordinated by closed-shell corrolato trianions and the higher state is composed of copper(II) ions chelated by open-shell corrolato dianions. The contributions from both states are evident in the molecular structure of monomeric

Ligand Noninnocence in Coinage Metal Corroles: A Silver Knife‐Edge

“…Similar bleaching of the Soret band is also observed for oneelectron oxidation of the Cu and Ag corroles (Figure 7). [16,32] By contrast, one-electron reduction of the Cu corroles resultsi n the appearance of new Soret bands with extinction coefficients that are comparable to or even highert han those of the neutral complexes, thus suggesting that the anionic states are aromatic and may be describeda sM II -corrole 3À .T hese observations are consistent with earlier studies, [32][33][34][35] in which we and www.chemeurj.org otherss howedt hat anionic Cu corroles may also be described similarly,t hat is, as Cu II -corrole 3À . Silver corroles were earlier shown to undergor eductive demetalation with exceptional ease.…”

Coordination chemistry of corroles with focus on main group elements

“…Cases in which not all N atoms participate in the bonding are quite rare, but exist in the cases of rhodium(I) [12,13], (oxo)vanadium(IV) and (oxo)titanium(IV) corroles [14]. 4-coordinate complexes that contain metal ions in their trivalent state are also rare, with the d 8 copper(III) and silver(III) corroles as the main exceptions [15,16]. The most commonly adopted coordination geometry of corroles is square pyramidal, because out of the N4 plane displacement of the metal ion is beneficial for both the metal and the corrole.…”

Synthesis and Photophysical and Electrochemical Study of Tyrosine Covalently Linked to High‐Valent Copper(III) and Manganese(IV) Complexes

“…In the case of [Cu(oec)] the dimerization occurred upon oxidation, and the first two oxidations involved two stepwise abstractions of one electron from each macrocycle in the electrogenerated corrole p -p dimer. It should be noted that also many triphenylcorrolato ligands show no evidence of dimerization [25] [31]. This means that the bulky substituents at the corrole macrocycle must have a significant effect on the electrooxidation mechanism, and the phenyl substituents at the corrole macrocycle preclude the formation of dimers.…”