RUTHENIUM PHTHALOCYANINE - STRUCTURE, MAGNETISM, ELECTRICAL-CONDUCTIVITY PROPERTIES, AND ROLE IN DIOXYGEN ACTIVATION AND OXYGEN-ATOM TRANSFER TO 1-OCTENE

Solid pure ruthenium phthalocyanine, obtained from its adduct [PcRu(DM SO)(2)].2DMSO, is an amorphous material, and its structure has been ex amined by the large-angle X-ray scattering (LAXS) technique. Experimen tal data are best fitted by assuming that ruthenium phthalocyanine is dimeric, i.e. (PcRu)(2), with a short intradimer Ru-(II)-Ru(II) contac t (2.40 Angstrom), six dimeric units, on average, closely approaching one another and stacked in a monodimensional array. (PcRu)(2) is param agnetic with a room-temperature magnetic moment (2.54 <mu(>)B), which is strongly temperature dependent in the range 300-6 K. Interpretation of the magnetic behavior leads to an electronic energy level diagram which locates the highest energy electrons for the dimer in the orbita l sequence sigma(2) pi(4) delta(2) delta(2) pi*(2). The electrical co nductivity value sigma(RT), 1 x 10(-5) Omega(-1) cm(-1) is also consid ered in the light of the structural features of the complex. (PcRu)(2) , stable to air as a solid material, easily interacts with dioxygen wh en in contact with tetrahydrofuran. Dioxygen activation and oxygen ato m transfer are observed for ruthenium phthalocyanine in the oxidation of 1-octene by O-2 in tetrahydrofuran, in the presence of (C6H5CN)(2)P dCl2 as the olefin activator, with selective formation of 2-octanone. Catalytic experiments were carried out at room temperature and at a p( O-2) of 50 atm. The optimized conditions for oxidation involve a Fe:Pd :olefin molar ratio of about 1:1.7:40.