Repozytorium

H1 NMR investigations of triphenylporphyrin metal complexes and electronic interactions in iron(III) complexes of meso-meso-linked 5,5'-bis(10,15,20-triphenylporphyrin).

Autorzy

Jacek Wojaczyński

Lechosław Latos-Grażyński

Piotr J. Chmielewski

P. Van Calcar

Alan L. Balch

Rok wydania

1999

Czasopismo

Inorganic Chemistry

Numer woluminu

38

Strony

3040-3050

DOI

10.1021/ic990038g

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

The 1H NMR spectra of iron(III) complexes of dimeric 5,5‘-bis(10,15,20-triphenylporphyrin) [(TrPPH2)2], 5,5‘-bis(10,15,20-tris(p-methoxyphenyl)porphyrin) [(Tr(p-MeOP)PH2)2], and hybrid (TrPPH2)(Tr(p-MeOP)PH2) and the respective monomeric 5,10,15-triphenylporphyrin (TrPPH2) and 5,10,15-tris(p-methoxyphenyl)porphyrin [Tr(p-MeOP)PH2] have been investigated in order to elucidate an impact of a direct mesomeso linkage on the electronic structure of corresponding high- and low-spin iron(III) porphyrins. The following species, covering the representative spin/oxidation states, have been investigated:  (TrPP)2(FeIIICl)2 (high spin); [(TrPP)2(FeIII(CN)2)2]2- (low spin); [(TrPP)2(FeIIICl)2]+ (high-spin iron(III), diporphyrin radical); [(TrPP)2(FeIIICl)2]2+ (high-spin iron(III), diradical of diporphyrin). The iron(III) diporphyrins (TrPP)2(FeIIICl)2, [(TrPP)2(FeIII(CN)2)2]2-, {[(TrPP)FeIII(CN)2][(Tr(p-MeOP)P)FeIII(CN)2]}2-, and [(TrPP)2(FeIIICl)2]2+ revealed the 1H NMR features which have been typically encountered in the spectra of the relevant monomeric complexes. Thus magnetic interactions between two subunits via skeleton appear to be minor. The characteristic broadening and/or paramagnetic shifts of 3-H and 7-H resonances were determined and are diagnostic features of the mesomeso linkage. One-electron, ligand-based oxidation of (TrPP)2(FeIIICl)2 to produce [(TrPP)2(FeIIICl)2]+ was observed with the unpaired electron delocalized over both macrocycles. The structure of (Tr(p-MeOP)P)ZnII·0.4CH2Cl2, the fundamental building block in synthesis of diporphyrins, was determined by X-ray crystallography. (Tr(p-MeOP)P)ZnII crystallizes in the monoclinic space group C2/c with a = 47.744(9) Å, b = 9.090(2) Å, c = 15.571(2) Å, β = 93.770(13)°, and Z = 8. The refinement of 494 parameters and 4361 reflections yields R1 = 0.0756, wR2 = 0.2169. The (Tr(p-MeOP)P)ZnII presents characteristic features of zinc(II) tetraphenylporphyrin. The molecular periphery of (Tr(p-MeOP)P)ZnII has a fully exposed meso position and two partially exposed pyrrole rings.

Słowa kluczowe

Group theory, Pyrroles, Ions, Nuclear magnetic resonance spectroscopy, Resonance structures

Adres publiczny

https://doi.org/10.1021/ic990038g

Strona internetowa wydawcy

https://www.acs.org/content/acs/en.html

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