TY - JOUR
T1 - Mono- and binuclear ruthenium corroles
T2 - Synthesis, spectroscopy, electrochemistry, and structural characterization
AU - Simkhovich, Liliya
AU - Luobeznova, Inna
AU - Goldberg, Israel
AU - Gross, Zeev
PY - 2003/1/3
Y1 - 2003/1/3
N2 - The aim of this research was to prepare mononuclear ruthenium corroles, because of the well-documented potency of analogous porphyrin complexes in catalysis. The syntheses of the mononuclear nitrosyl complexes [Ru(tpfc)(NO)] and [Ru(tdcc)(NO)] (tpfc=trianion of 5,10,15-tris(pentafluorophenyl)corrole, tdcc=trianion of 5,10,15-tris(2,6-dichlorophenyl)corrole), and of the binuclear [{Ru(tpfc)}2] were achieved by using [{Ru(cod)Cl2}x] (cod=cyclooctadiene) as the metal source. The NMR spectra of all three complexes clearly demonstrate that they are diamagnetic; this is consistent with a triple bond between the metal ions in [{Ru(tpfc)}2] and is expected for classical {MNO}6 complexes. These features were further substantiated by the stretching frequencies of the {MNO} moieties, electrochemical measurements on all complexes, and the X-ray crystal structures of [Ru(tpfc)(NO)] and [{Ru(tpfc)}2]. A comparison of the spectroscopic and structural characteristics of these new complexes with analogous iron corroles, as well as with iron and ruthenium porphyrins, suggests that it will be hard to obtain mononuclear ruthenium corroles without π-accepting ligands.
AB - The aim of this research was to prepare mononuclear ruthenium corroles, because of the well-documented potency of analogous porphyrin complexes in catalysis. The syntheses of the mononuclear nitrosyl complexes [Ru(tpfc)(NO)] and [Ru(tdcc)(NO)] (tpfc=trianion of 5,10,15-tris(pentafluorophenyl)corrole, tdcc=trianion of 5,10,15-tris(2,6-dichlorophenyl)corrole), and of the binuclear [{Ru(tpfc)}2] were achieved by using [{Ru(cod)Cl2}x] (cod=cyclooctadiene) as the metal source. The NMR spectra of all three complexes clearly demonstrate that they are diamagnetic; this is consistent with a triple bond between the metal ions in [{Ru(tpfc)}2] and is expected for classical {MNO}6 complexes. These features were further substantiated by the stretching frequencies of the {MNO} moieties, electrochemical measurements on all complexes, and the X-ray crystal structures of [Ru(tpfc)(NO)] and [{Ru(tpfc)}2]. A comparison of the spectroscopic and structural characteristics of these new complexes with analogous iron corroles, as well as with iron and ruthenium porphyrins, suggests that it will be hard to obtain mononuclear ruthenium corroles without π-accepting ligands.
KW - Cyclic voltammetry
KW - Iron
KW - NMR spectroscopy
KW - Porphyrinoids
KW - Ruthenium
KW - X-ray diffraction
UR - http://www.scopus.com/inward/record.url?scp=0037415098&partnerID=8YFLogxK
U2 - 10.1002/chem.200390013
DO - 10.1002/chem.200390013
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C2 - 12506376
AN - SCOPUS:0037415098
SN - 0947-6539
VL - 9
SP - 201
EP - 208
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 1
ER -