147342-56-1Relevant academic research and scientific papers
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,Bandoli, Giuliano,Dolmella, Alessandro,Boschi, Tristano
, p. 1171 - 1176 (2008/10/08)
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 exampleof 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 P1, with a = 10.628(2) A?, b = 11.585(2) A?, c = 22.352(4) A?, α = 84.93(2)°, β = 78.56(2)°, γ = 72.93(2)°, 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 [Fo > 4 σ(Fo)]. 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 A?, with the largest deviations being +0.33 and -0.33 A? 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.
