Magnetic properties and molecular structures of binuclear (2-pyrazinecarboxylate)-bridged complexes containing Re(IV) and M(II) (M = Co, Ni)

Three novel Re(iv) compounds, the mononuclear complex Bu(4)NReBr(5)(Hpyzc)] (1) and the heterobimetallic complexes ReBr(5)(mu-pyzc)M(dmphen)(2)].2CH(3)CN M = Co (2), Ni (3)] (Hpyzc = 2-pyrazinecarboxylic acid, dmphen = 2,9-dimethyl-1,10-phenanthroline), have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. The structure of 1 consists of ReBr(5)(Hpyzc)](-) complex anions and tetrabutylammonium cations, Bu(4)N(+). The Re(iv) is surrounded by five bromide anions and a N-donor Hpyzc monodentate ligand, in a distorted octahedral environment. The structures of 2 and 3 consist of dinuclear units ReBr(5)(mu-pyzc)M(dmphen)(2)], with the metal ions linked by a pyzc bridge ligand, being bidentate toward M(II) and monodentate toward Re(IV). The environment of Re(IV) is the same as in 1, whereas M(II) is six-coordinate, being surrounded by four nitrogen atoms of two bidentate dmphen ligands and one oxygen atom and one nitrogen atom of the pyzc anion. The magnetic properties of 1-3 were investigated in the temperature range 2.0-300 K. 1 shows the expected magnetic behavior for a mononuclear Re(IV) complex with a weak intermolecular antiferromagnetic coupling at low temperatures. The bimetallic complexes exhibit an intramolecular ferromagnetic coupling between Re(IV) and the M(II) ion (Co, Ni).