Synthesis and characterization of free-base, copper, and nickel isocorroles.
A series of free-base and metalated isocorroles represented as (TT-n-iso-Cor)H(2) and (TT-n-iso-Cor)M(II), where n = 5 or 10 and M = Ni or Cu, were synthesized and characterized by electrochemistry and spectroelectrochemistry in CH(2)Cl(2) containing 0.1 M tetra-n-butylammonium perchlorate. The metalation of the free-base macrocycles with Co(II), Mn(III), or Zn(II) was also attempted but was unsuccessful. Six isocorroles were isolated and shown to undergo two stepwise oxidations to give pi-cation radicals and dications in CH(2)Cl(2), with the most stable products being obtained in the case of the 10-substituted derivatives. The same isocorroles could also be reduced by one or two electrons, but the initial one-electron addition products are unstable and undergo a rapid chemical reaction giving a reduced corrole or corrole-like product, which could be reoxidized to the corresponding (TTCor)M at a controlled positive potential. This series of reactions effectively illustrates an isocorrole to corrole conversion upon reduction and reoxidation and was monitored by both electrochemistry and thin-layer spectroelectrochemistry.
Pomarico
Giuseppe
G
Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, via della Ricerca Scientifica, 1, 00133 Rome, Italy.
Xiao
Xiao
X
Nardis
Sara
S
Paolesse
Roberto
R
Fronczek
Frank R
FR
Smith
Kevin M
KM
Fang
Yuanyuan
Y
Ou
Zhongping
Z
Kadish
Karl M
KM
D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D008665:Metalloporphyrins / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
D008665:Metalloporphyrins; D009942:Organometallic Compounds; D003300:Copper; D009532:Nickel