TY - JOUR
T1 - Homo-/heterotrinuclear mixed-valent oxo-centered iron/nickel clusters-mössbauer studies on internal electron-exchange processes
AU - Saalfrank, Rolf W.
AU - Scheurer, Andreas
AU - Reimann, Uwe
AU - Hampel, Frank
AU - Trieflinger, Christian
AU - Büschel, Michael
AU - Daub, Jörg
AU - Trautwein, Alfred X.
AU - Schünemann, Volker
AU - Coropceanu, Veaceslav
PY - 2005/10/7
Y1 - 2005/10/7
N2 - In a one-pot reaction of N-(5-methylthiazole-2-yl)-thiazole-2-carboxamide HL2 (3) with iron(II) acetate in air, the homotrinuclear heteroleptic mixed-valent oxo-centered iron cluster [FeIIFe2 IIIO(L2)3(OAc)3] (4) was formed. Exchange of iron(II) in 4 by nickel(II) afforded the heteronuclear cluster [NiIIFe2IIIO(L2)3(OAc) 3] (6). To obtain crystals suitable for X-ray structure analyses, in 4 and 6, the OAc- co-ligands were exchanged by OBz ligands to give [FeIIFe2IIIO(L2)3(OBz) 3] (5) and [NiIIFe2IIIO(L 2)3(OBz)3] (7). The complexes 5 and 7 are isostructural and made up of three ditopic, tridentate ligands (L 2)- and three bridging benzoate co-ligands, which fix the three metal ions in the corners of a triangle with an μ3-O 2- ion in the center. The mixed-valent character of 4-7, their intramolecular electron-exchange processes, and their redox properties were studied by variable-temperature Mössbauer spectroscopy and cyclic voltammetry.
AB - In a one-pot reaction of N-(5-methylthiazole-2-yl)-thiazole-2-carboxamide HL2 (3) with iron(II) acetate in air, the homotrinuclear heteroleptic mixed-valent oxo-centered iron cluster [FeIIFe2 IIIO(L2)3(OAc)3] (4) was formed. Exchange of iron(II) in 4 by nickel(II) afforded the heteronuclear cluster [NiIIFe2IIIO(L2)3(OAc) 3] (6). To obtain crystals suitable for X-ray structure analyses, in 4 and 6, the OAc- co-ligands were exchanged by OBz ligands to give [FeIIFe2IIIO(L2)3(OBz) 3] (5) and [NiIIFe2IIIO(L 2)3(OBz)3] (7). The complexes 5 and 7 are isostructural and made up of three ditopic, tridentate ligands (L 2)- and three bridging benzoate co-ligands, which fix the three metal ions in the corners of a triangle with an μ3-O 2- ion in the center. The mixed-valent character of 4-7, their intramolecular electron-exchange processes, and their redox properties were studied by variable-temperature Mössbauer spectroscopy and cyclic voltammetry.
UR - http://www.scopus.com/inward/record.url?scp=26844475093&partnerID=8YFLogxK
U2 - 10.1002/chem.200500097
DO - 10.1002/chem.200500097
M3 - Journal articles
AN - SCOPUS:26844475093
SN - 0947-6539
VL - 11
SP - 5843
EP - 5848
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 20
ER -
