The first synthesis of the corrole ring by self-condensation of a monopyrrolic unit is reported. The reaction occurs only in the presence of cobalt ions; it leads to the formation of (triphenylphosphine)(5,10,15-triphenyl-2,3,7,8,12, 13,17,18-octamethylcorrolato)cobalt(III), [Co(OMTPC)PPh3] and represents the first example of interconversion between a porphyrinoid and a corrole structure. Crystals of [Co(OMTPC)PPh3].CH2Cl2 have been obtained by slow diffusion of methanol into a dichloromethane solution of the complex and have been characterized by single-crystal X-ray analysis. They crystallize in the triclinic system, space group P1BAR, with a = 10.628 (2) angstrom, b = 11.585(2) angstrom, c = 22.352(4) angstrom, alpha = 84.93(2)-degrees, beta = 78.56(2)-degrees, gamma = 72.93(2)-degrees, and Z = 2. The structure was solved by heavy-atom methods and refined by least-square techniques to R = 0.051 for 6377 unique data [F(o) > 4 sigma(F(o))]. The analysis reveals the substantial planarity of the macrocyclic ring. In the 23-atom core of the corrole moiety each atom shows an average displacement from the plane of best fit of 0.14 angstrom, with the largest deviations being +0.33 and -0.33 angstrom for C(2) and C(12), respectively. The synthesis of diphenyl derivatives of corrole: (triphenylphosphine) (5,10-diphenyl-2,3,7,8,12,13,17,18-octamethylcorrolato)cobalt(III), [Co(5,10-OMDPC)PPh3], and (triphenylphosphine) (5,15-diphenyl-2,3,7,8,12,13,17,18-octamethylcorrolato)cobalt(III), [Co(5,15-OMDPC)PPh3], is also reported. Plausible reaction pathways leading to the formation of the two isomers are discussed together with the spectral properties of the complexes.

Paolesse, R., Licoccia, S., Bandoli, G., Dolmella, A., Boschi, T. (1994). First direct synthesis of a corrole ring from a monopyrrolic precursor. Crystal and molecular structure of (triphenylphosphine)-(5,10,15-triphenyl-2,3,7,8,12,13,17,18-octamethylcorrolato) cobalt(III)-dichloromethane. INORGANIC CHEMISTRY, 33(6), 1171-1176.

First direct synthesis of a corrole ring from a monopyrrolic precursor. Crystal and molecular structure of (triphenylphosphine)-(5,10,15-triphenyl-2,3,7,8,12,13,17,18-octamethylcorrolato) cobalt(III)-dichloromethane

PAOLESSE, ROBERTO;LICOCCIA, SILVIA;
1994-01-01

Abstract

The first synthesis of the corrole ring by self-condensation of a monopyrrolic unit is reported. The reaction occurs only in the presence of cobalt ions; it leads to the formation of (triphenylphosphine)(5,10,15-triphenyl-2,3,7,8,12, 13,17,18-octamethylcorrolato)cobalt(III), [Co(OMTPC)PPh3] and represents the first example of interconversion between a porphyrinoid and a corrole structure. Crystals of [Co(OMTPC)PPh3].CH2Cl2 have been obtained by slow diffusion of methanol into a dichloromethane solution of the complex and have been characterized by single-crystal X-ray analysis. They crystallize in the triclinic system, space group P1BAR, with a = 10.628 (2) angstrom, b = 11.585(2) angstrom, c = 22.352(4) angstrom, alpha = 84.93(2)-degrees, beta = 78.56(2)-degrees, gamma = 72.93(2)-degrees, and Z = 2. The structure was solved by heavy-atom methods and refined by least-square techniques to R = 0.051 for 6377 unique data [F(o) > 4 sigma(F(o))]. The analysis reveals the substantial planarity of the macrocyclic ring. In the 23-atom core of the corrole moiety each atom shows an average displacement from the plane of best fit of 0.14 angstrom, with the largest deviations being +0.33 and -0.33 angstrom for C(2) and C(12), respectively. The synthesis of diphenyl derivatives of corrole: (triphenylphosphine) (5,10-diphenyl-2,3,7,8,12,13,17,18-octamethylcorrolato)cobalt(III), [Co(5,10-OMDPC)PPh3], and (triphenylphosphine) (5,15-diphenyl-2,3,7,8,12,13,17,18-octamethylcorrolato)cobalt(III), [Co(5,15-OMDPC)PPh3], is also reported. Plausible reaction pathways leading to the formation of the two isomers are discussed together with the spectral properties of the complexes.
Pubblicato
Rilevanza internazionale
Articolo
Sì, ma tipo non specificato
Settore CHIM/07 - Fondamenti Chimici delle Tecnologie
English
Con Impact Factor ISI
METAL-COMPLEXES; VITAMIN-B12; PORPHYRINS
Paolesse, R., Licoccia, S., Bandoli, G., Dolmella, A., Boschi, T. (1994). First direct synthesis of a corrole ring from a monopyrrolic precursor. Crystal and molecular structure of (triphenylphosphine)-(5,10,15-triphenyl-2,3,7,8,12,13,17,18-octamethylcorrolato) cobalt(III)-dichloromethane. INORGANIC CHEMISTRY, 33(6), 1171-1176.
Paolesse, R; Licoccia, S; Bandoli, G; Dolmella, A; Boschi, T
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/53276
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