Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence

High-resolution crystal structure of cytochrome P450cam.

Reactivity of Dioxygen−Copper Systems

1,1‘-Binaphthyl Dimers, Oligomers, and Polymers: Molecular Recognition, Asymmetric Catalysis, and New Materials†

On the function and mechanism of action of peroxidases

Reversible oxygen adduct formation in cobalt(II) picket fence porphyrins

Condensation of 1,2-dicyanobenzene and 2-amino-4-methylpyridine resulted in the formation of a ligand, 4'-MeLH, which in its anionic form functions as a tridentate chelate. Metal complexes were prepared with metal to ligand ratios of 1:1 and 1:2. The 1:1 complexes also contain acetate as a ligand while in the 1:2 complex the two tridentate ligands provide a pseudooctahedral environment about the metal ion. An analogous binucleating ligand was prepared by reaction of 1,2,4,5-tetracyanobenzene and 2-amino-4-sec-butylpyridine. This ligand, as a dianion, is capable of binding two metal ions, providing three coordination sites for each. Complexes were prepared in which the remaining coordination sites are occupied either by 4'-MeLH, resulting in two six-coordinate metal ions, or by an acetate ligand. Mononuclear and binuclear complexes were prepared with Mn(II), Fe(II), Co(II), Co(III), Ni(II), Cu(II), and Zn(II). Magnetic, spectral, and electrochemical properties of these molecules were investigated.

Mononuclear and binuclear metal complexes of 1,3-bis(2-pyridylimino)isoindolines

The ruthenium complex (1,3-bis(4-methyl-2-pyridylimino)isoindoline) trichlororuthenium III catalyzes the autoxidation and electrochemical oxidation of alcohols in basic solution. The reaction is general, resulting in the oxidation of primary and secondary alcohols, with the principal products being aldehydes and ketones. The catalytic autoxidation is affected by the strength of the base used and its coordinating ability. The best results were obtained with sodium ethoxide as a base. Turnover numbers of 10-30 per day were observed in 1 atm of oxygen at ambient temperature, with larger turnover numbers at higher temperature. More than 200 turnovers were observed in the oxidation of ethanol at the ambient temperature with little or no loss of catalytic activity. The catalyzed electrochemical oxidation was carried out in an alcoholic solution containing 2,6-lutidine with a carbon electrode at 0.8-1.0 V vs. NHE. In the absence of catalyst, negligible current was observed. More than 20 catalytic cycles were completed with the current remaining at 75% of its initial value. The ruthenium III complex exhibits reversible one-electron oxidation waves in non-alcoholic solvents in the presence or absence of 2,6-lutidine. Possible pathways for the catalytic autoxidation and electrochemical oxidation are presented.

Ruthenium complexes of 1,3‐bis(2‐pyridylimino)isoindolines as alcohol oxidation catalysts

Reaction of molecular oxygen with copper(I). Structural characterization of dimeric .mu.-carbonato and tetrameric .mu.-hydroxo complexes resulting from the autoxidation of a copper(I) carbonyl complex

Synthesis and structure of (N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine)dicopper(I) and its dicarbonyl adduct

Robert R. Gagne

Papers

Reversible oxygen adduct formation in cobalt(II) picket fence porphyrins

Mononuclear and binuclear metal complexes of 1,3-bis(2-pyridylimino)isoindolines

Ruthenium complexes of 1,3‐bis(2‐pyridylimino)isoindolines as alcohol oxidation catalysts

Reaction of molecular oxygen with copper(I). Structural characterization of dimeric .mu.-carbonato and tetrameric .mu.-hydroxo complexes resulting from the autoxidation of a copper(I) carbonyl complex

Synthesis and structure of (N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine)dicopper(I) and its dicarbonyl adduct