ABSTRACT
The interaction of manganese(ii) phthalocyanine with 7,7,8,8-tetracyanoquinodimethane and its perfluoro derivative proceeds with the oxidation of Mn and the reduction of the acceptor molecules to give the first mixed single crystals of manganese(iii) phthalocyanine with TCNQ/F4-TCNQ radical anions. The crystals have unusual structures with C-Hπ interactions between the ions and their orthogonal arrangement, as well as remarkable redox properties. The charge transfer was proved by spectroscopic and magnetic studies.
ABSTRACT
The interplay of NMR experiments and DFT calculations of NMR parameters is a reliable method for determining the relative configurations of pentacoordinate chiral spirophosphoranes bearing two six- or five-membered rings at the phosphorus atom in solution. The major product of the Betti based derivatives corresponds to the isomers with both substituents at chiral carbons being opposite to the P-H proton. The next populated product corresponds to the isomer with different chiralities at carbons. The least populated isomer is one with both substituents being at the same side of the heterocycle as the P-H bond.
ABSTRACT
A new diastereoselective synthesis of alpha-aminophosphonates has been developed, based on the reaction, in the presence of trifluoroacetic acid, of trialkyl phosphites with chiral imines derived from (R)- or (S)-1-(alpha-aminobenzyl)-2-naphthol. The reaction proceeds at room temperature in toluene with high diastereoselectivity. The major diastereomer can be separated by crystallization from an appropriate solvent. The relative configuration of both chiral centers of the major diastereomer was determined by single-crystal X-ray structure analysis. The desired alpha-aminophosphonic acids can be obtained in enantiopure form by treatment of the corresponding diastereomers with HCl.
