ChemInform Abstract: Structural and Chemical Properties of a Reactive Metalloporphyrin with Aliphatic Amine N-Oxide Axial Ligands. Crystal and Molecular Structure of Bis(N-methylmorpholine N-oxide)(tetraphenylporphinato)manganese(III) Perchlorate.
Abstract
High-spin (S = 2) Mn(III) porphyrin complexes (I) with either strongly or weakly coordinating anionic axial counterions can catalyze the oxygenation of both alkenes or alkanes by aliphatic amine N-oxides at temp. down to 25 °C in nonpolar solvents.
ChemInform Abstract
High-spin (S = 2) Mn(III) porphyrin complexes (I) with either strongly or weakly coordinating anionic axial counterions can catalyze the oxygenation of both alkenes or alkanes by aliphatic amine N-oxides at temp. down to 25 °C in nonpolar solvents. The N-oxide (II) not only reacts readily with Mn porphyrins to transfer oxygen as described above, but also forms a reactive isolable complex (III) (no yield given), which is isolated under conditions which prevent decomposition and hydrocarbon oxidation. (III) is characterized by its crystal structure (space group Pccn, Z=4). The stoichiometric reactions of (III) with representative alkenes (IV), (VI), and (X) and the alkane (XI) are contrasted to catalytic oxygenations of the same substrates (as demonstrated by the reaction of (IV)) using a large excess of the oxygen donor (II) and (Ia) as the catalyst. The product distribution for both reactions are similar.
