Résultat de la recherche
Ru2(CO)4(OOCR)2L2 sawhorse-type complexes containing axial 5-(4-pyridyl)-10,15,20-triphenylporphyrin ligands
The thermal reaction of Ru3(CO)12 with various carboxylic acids (benzoic, 4-hydroxyphenylacetic, ferrocenic, stearic, oleic, 4-(octadecyloxy)benzoic) in refluxing tetrahydrofuran, followed by addition of 5-(4-pyridyl)-10,15,20-triphenylporphyrin (L), gives the dinuclear complexes Ru2(CO)4(OOCR)2L2 (1: R = –C6H5, 2: R = –CH2-p-C6H4OH, 3: R = –C5H4FeC5H5, 4: R = –(CH2)16CH3, 5: R = –(CH2)7CHdouble bond; length as m-dashCH(CH2)7CH3, 6: R = –p-C6H4O(CH2)17CH3). Complexes 1–6 were characterised by IR, NMR, and ESI-MS as well as by elemental analysis. The UV–Vis spectra show the Soret band centred at 417 nm and the Q bands at 515, 550, 590 and 645 nm, respectively.
Dinuclear ruthenium sawhorse-type complexes containing bridging ligands with ferrocenyl substituents in endo/endo, endo/exo and exo/exo orientations
The dinuclear ruthenium complexes Ru2(CO)4(OOCC5H4FeC5H5)2L2 (L = NC5H5: 1, L = PPh3: 2) have been synthesized from Ru3(CO)12, ferrocene carboxylic acid and pyridine or triphenylphosphine, respectively. The single-crystal X-ray structure analysis reveals for 1 and 2 a Ru2(CO)4 sawhorse backbone with the two ferrocenyl substituents of the two carboxylato bridges being endo/exo with respect to each other in the solid state. With the new pyridine derivative NC5H4OOCC5H4FeC5H5 (4-ferrocenoyl pyridine) (3) as axial ligand, the complex Ru2(CO)4(OOCC5H4FeC5H5)2(NC5H4OOCC5H4FeC5H5)2 (4) was obtained, the single crystal X-ray structure analysis showing an exo/exo orientation of the two carboxylato bridges in the solid state. The endo/endo orientation is found in the solid-state structure of Ru2(CO)4(HNOCC5H4FeC5H5)2(PPh3)2 (5), the two OCNH bridges being transoïd with respect to each other; this complex is accessible from Ru3(CO)12, ferrocenamide and triphenylphosphine.
New Dinuclear Ru2(CO)4 Sawhorse-Type Complexes Containing Bridging Carboxylato Ligands
The thermal reaction of Ru3(CO)12 with ethacrynic acid, 4-[bis(2-chlorethyl)amino]benzenebutanoic acid (chlorambucil), or 4-phenylbutyric acid in refluxing solvents, followed by addition of two-electron donor ligands (L), gives the diruthenium complexes Ru2 (CO)4(O2CR)2L2 (1: R = CH2O-C6H2Cl2-COC(CH2)C2H5, L = C5H5N; 2: R = CH2O-C6H2Cl2-COC(CH2)C2H5, L = PPh3; 3: R = C3H6-C6H4-N(C2H4-Cl)2, L = C5H5N; 4: R = C3H6-C6H4-N(C2H4-Cl)2, L = PPh3; 5: R = C3H6-C6H5, L = C5H5N; 6: R = C3H6-C6H5, L = PPh3). The single-crystal structure analyses of 2, 3, 5 and 6 reveal a dinuclear Ru2(CO)4 sawhorse structure, the diruthenium backbone being bridged by the carboxylato ligands, while the two L ligands occupy the axial positions of the diruthenium unit.
Synthesis, structure and electrochemistry of cationic diruthenium complexes of the type [(N∩N)2Ru2 (CO)2 (μ-CO)2(μ-OOCFc)]+ containing a ferrocenecarboxylato bridge and two chelating aromatic diimine ligands
The dinuclear bis(ferrocenecarboxylato) complex Ru2 (CO)4 (μ-OOCFc)2 (py)2 (Fc = ferrocenyl, py = pyridine) was found to react with aromatic diimines (2,2′-dipyridyl, 4,4′-dimethyl-2,2′-dipyridyl, 1,10-phenanthroline, 5-nitro-1,10-phenanthroline, and 5-amino-1,10-phenanthroline) in methanol to give the cationic diruthenium complexes [(N∩N)2Ru2 (CO)2 (μ-CO)2(μ-OOCFc)]+ (1: N∩N = 2,2′-dipyridyl, 2: N∩N = 4,4′-dimethyl-2,2′-dipyridyl, 3: N∩N = 1,10-phenanthroline, 4: N∩N = 5-nitro-1,10-phenanthroline, 5: N∩N = 5-amino-1,10-phenanthroline), which have been isolated as the hexafluorophosphate salts. The molecular structure of 3, solved by single-crystal X-ray analysis of the tetraphenylborate salt [3][BPh4], shows a diruthenium backbone bridged by two carbonyl and by one ferrocenecarboxylato ligand, the two 1,10-phenanthroline ligands being in the axial positions. Cyclic voltammetry in dichloromethane reveals for all compounds two successive oxidations due to ferrocene/ferrocenium redox couple and oxidation of the diruthenium core.