Copper complexes corroles

Copper corrole is a diamagnetic copper(III) complex which at higher temperatures exists in the triplet state and is then best formulated as a copper(II) corrole-n-radical. 

It was found that addition of hydroxide anion in dimethylformamide or dimethylsulfoxide to metal(II) corrole complexes results in the appearance of much sharper absorption bands relative to the starting compounds. These findings were considered consistent with the idea that an anionic, 18 Jt-electron aromatic corrole complex (e.g., 2.119) is formed as the result of what appears to be a formal deprotonation process (Scheme 2.1.25). That deprotonation actually occurs was inferred from acid-base titrations involving nickel(II) and copper(II) corroles. The conclusion that these species are anionic aromatic compounds came from an appreciation that their electronic spectra resemble those recorded for divalent metallo-porphyrins. In any event, the anion that results was found to be quenched upon acidification, regenerating the corresponding non-aromatic metallocorroles. ... 

Group 11. Paramagnetic (1H, 15N) NMR spectra were used to study a Cu -IDA (=iminodiacetic acid) complex localised on a protein surface. H and 13C NMR spectra were reported for copper(II) bis-benzimidazole complexes.1225 Variable temperature H NMR spectra of copper complexes of p-octafluorinated triarylcorroles reveal a thermally-accessible paramagnetic excited state, i.e. a Cu11 corrole 7i-cation radical.1226 Copper(II) forms of stellacyanin from Rhus vernicifera were characterised by H NMR.1227... 

Abstract The transition metal complexes of the non-innocent, electron-rich corrole macrocycle are discussed. A detailed summary of the investigations to determine the physical oxidation states of formally iron(IV) and cobalt(IV) corroles as well as formally copper(III) corroles is presented. Electronic structures and reactivity of other metallocorroles are also discussed, and comparisons between corrole and porphyrin complexes are made where data are available. The growing assortment of second-row corrole complexes is discussed and compared to first-row analogs, and work describing the synthesis and characterization of third-row corroles is summarized. Emphasis is placed on the role of spectroscopic and computational studies in elucidating oxidation states and electronic configurations. 

Luobeznova I, Simkhovich L, Goldberg I, Gross Z (2004) Electronic structures and reactivities of corrole-copper complexes. Eur J Inorg Chem 1724-1732... 

Figure 10.12 2,17-Bis-sulfonato-5,10,15-tri(pentafluorophenyl)corrole manganese complex 14 [59,60], tetrakis(sulfonato) phthalocyanin copper complex 15 [61], and meso-tetrakis (p-carboxyphenyl)-porphyrln manganese complex 16 [62].

The reaction of corrole 2.82 with copper(II) acetate was also found to produce a neutral complex that is spectroscopically identical to that previously described. In this case, however, the complex that results was assigned structure 2.181, wherein oxidation of the metal center from + 2 to +3 appears to have occurred (Scheme 2.1.58). This is in marked contrast to the two previous structural assignments (i.e.. 

Fig. 13 The crystal structure of a highly saddled copper [3-octabrominated corrole complex (left) and the predicted saddling angles for a number of mero-triaryl-substituted copper corroles. Reprinted with permission from [171]. Copyright 2010 American Chemical Society...

Ghosh A, Wondimagegn T, Parusel ABJ (2000) Electronic structure of gallium, copper, and nickel complexes of corrole high-valent transition metal centers versus non-innocent ligands. J Am Chem Soc 122 5100-5104... 

Will S, Lex J, Vogel E, Schmickler H, Gisselbrecht JP, Haubtmann C, Bernard M, Gross M (1997) Nickel and copper corroles well-known complexes in a new light. Angew Chem Int Ed Engl 36 357-361... 

Thomas KE, Wasbotten IH, Ghosh A (2008) Copper P-octakis(trifluoromethyl)corroles new paradigms for ligand substituent effects in transition metal complexes. Inorg Chem 47 10469-10478... 

Unexpectedly large Vff couplings of about 14 Hz, apparently a manifestation of the highly crowded structure, have been observed by Thomas et al. in four copper -octakis(trifluoromethyl)corrole complexes. 

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