Quimica

Inorg. Chem. 1994, 33, 4635-4640

4635

Ruthenium Phthalocyanine: Structure, Magnetism, Electrical Conductivity Properties, and Role in Dioxygen Activation and Oxygen Atom Transfer to 1-Octene
A. Capobianchi2 A. M. Paoletti,? G. Pennesi? G. Rossi,*JR. Caminiti,* and C. Ercolani*>*
ICMAT (CNR), Area della Ricerca di Roma, C. P. 10, 00016 Monterotondo Stazione, Italy, and Dipartimento di Chimica, Universith La Sapienza, p.le A. Mor0 5 , 00185 Roma, Italy
Received November 4, 1993@

Solid pure ruthenium phthalocyanine, obtained from its adduct [PcRu(DMS0)2)2DMSO, is an amorphous material, and its structure has been examined by the large-angle X-ray scattering (LAXS) technique. Experimental data are best fitted by assuming that ruthenium phthalocyanine is dimeric, Le. (PcRu)z, with a short intradimer Ru(11)-Ru(I1) contact (2.40 A), six dimeric units, on average, closely approaching one another and stacked in a monodimensional array. (PcRu)2 is paramagnetic with a room-temperature magnetic moment (2.54 clg), 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 orbital sequence ~ ~ d d ~ d * ~ The * . n * electrical conductivity value o(RT), 1 x SZ-’ cm-’, is also considered in the light of the structural features of the complex. (PcRu)z, stable to air as a solid material, easily interacts with dioxygen when in contact with tetrahydrofuran. Dioxygen activation and oxygen atom transfer are observed for ruthenium phthalocyanine in the oxidation of 1-octene by 0 2 in tetrahydrofuran, in the presence of (C6HsCN)2PdC12 as the olefin activator, with selective formation of 2-octanone. Catalytic experiments were carried out at room temperature and at a ~ ( 0 2 of 50 atm. The optimized conditions for oxidation involve a Fe:Pd:olefin molar ratio of about ) 1:1.7:40.

Introduction
Reexamination of previous