V. V. Bashilov

Synthesis, NMR study, partial resolution and redox-demercuration of chiral 2-bromomercuri-4-dimethylaminobutane

Abstract The preparation and 1H, 13C NMR spectra are reported for chiral 2-bromomercuri-4-dimethylaminobutane (A), a novel useful organomercurial model having both a mercury atom attached to a chiral carbon centre and a tertiary nitrogen in the γ-position. Racemic A has been resolved partially using dibenzoyl-d tartaric acid. Redox-demercuration with a palladium(0) complex was shown to give an optically active palladium metallocycle (B), the signs of optical rotation of A and B being the same.

Fullerenes covalently linked to transition metals with organic ligands

Synthesis of molecules combining both fullerene and metallocene moieties separated by some spacer is discussed in connection with the possible intramolecular charge transfer. Two new kinds of spacers, =CH-CO- and -Pd-P-, have been introduced by using the corresponding reactions. Reaction of diazoacetyl ferrocene and cymantrene with C60 has been studied in detail and products characterized. 1,1-Bis (diazoacetyl) ferrocene gave with C60 1:1 adduct to which the ansa-structure has been assigned on the basis of 1H and 13C NMR spectra. Palladium-h2-C60 complex with a bidentate ferrocenyl diphosphine as a ligand has been also prepared.

First optically active P-alkoxy derivative of palladated phosphacymantrene: synthesis, structure, and chiroptical properties

The solvopalladation reaction of 2,5-diphenylphosphacymantrene with Na2PdCl4, AcONa, and optically active carbinol (S)-(−)-2-methylbutanol was carried out. Optically active complex 3 was obtained and characterized by X-ray diffraction analysis and circular dichroism (CD), 13C and 31P NMR, IR, and UV spectra.