TY - JOUR
T1 - Synthesis and crystal structure of an unexpected anionic trinuclear cobalt(III) complex with ferrocenyl-containing tridentate ONO donor Schiff base ligands
AU - Novoa, Néstor
AU - Dorcet, Vincent
AU - Sinbandhit, Sourisak
AU - Manzur, Carolina
AU - Carrillo, David
AU - Hamon, Jean René
N1 - Publisher Copyright:
© 2014 Taylor & Francis.
PY - 2014
Y1 - 2014
N2 - The tridentate ONO-donor Schiff base ligand derived from the condensation of 1-ferrocenyl-1,3-butanedione and 2-aminophenol, generated in situ and treated further with potassium tert-butoxide, reacted in THF with Co(NO3)2·6H2O in the presence of pyridine to afford the ionic complex [{(η5-C5H5)Fe(η5-C5H4)-C(O)CH=C(CH3)N-C6H4-2-O}2Co(III)]-[K(HOCH2CH3)2]+ (1, 50% yield). Compound 1 was characterized by elemental analysis, FT-IR, and multidimensional 1H and 13C NMR spectroscopy. Single-crystal X-ray diffraction reveals that the two metalloligands are meridionally coordinated to a Co(III) ion that adopts a slightly distorted octahedral geometry. The doubly solvated potassium counter-ion is asymmetrically positioned with respect to the two metalloligands. Such an arrangement allows the observation by 1H NMR of restricted rotation of the ferrocenyl units and the splitting of both carbonyl and imine carbons, thus suggesting that the structure observed in the solid state is retained in solution. Complex 1 exhibits in its cyclic voltammetry curve two anodic reversible waves attributed to the oxidation of Co(III)-phenolates into Co(III)-phenoxyl radical and that of the ferrocenyl fragment into its ferrocenium counterpart.
AB - The tridentate ONO-donor Schiff base ligand derived from the condensation of 1-ferrocenyl-1,3-butanedione and 2-aminophenol, generated in situ and treated further with potassium tert-butoxide, reacted in THF with Co(NO3)2·6H2O in the presence of pyridine to afford the ionic complex [{(η5-C5H5)Fe(η5-C5H4)-C(O)CH=C(CH3)N-C6H4-2-O}2Co(III)]-[K(HOCH2CH3)2]+ (1, 50% yield). Compound 1 was characterized by elemental analysis, FT-IR, and multidimensional 1H and 13C NMR spectroscopy. Single-crystal X-ray diffraction reveals that the two metalloligands are meridionally coordinated to a Co(III) ion that adopts a slightly distorted octahedral geometry. The doubly solvated potassium counter-ion is asymmetrically positioned with respect to the two metalloligands. Such an arrangement allows the observation by 1H NMR of restricted rotation of the ferrocenyl units and the splitting of both carbonyl and imine carbons, thus suggesting that the structure observed in the solid state is retained in solution. Complex 1 exhibits in its cyclic voltammetry curve two anodic reversible waves attributed to the oxidation of Co(III)-phenolates into Co(III)-phenoxyl radical and that of the ferrocenyl fragment into its ferrocenium counterpart.
KW - Cobalt(III) complex
KW - Crystal structure
KW - Ferrocenyl
KW - ONO ligand
KW - Schiff base
UR - http://www.scopus.com/inward/record.url?scp=84912027066&partnerID=8YFLogxK
U2 - 10.1080/00958972.2014.936406
DO - 10.1080/00958972.2014.936406
M3 - Article
AN - SCOPUS:84912027066
VL - 67
SP - 4101
EP - 4113
JO - Journal of Coordination Chemistry
JF - Journal of Coordination Chemistry
SN - 0095-8972
IS - 23-24
ER -