SOLVENT DEPENDENCY OF SUBSTITUTION REACTIONS OF OXORHENIUM(V) COMPLEXES. THE CRYSTAL STRUCTURES OF TRANS-DICHLORO (N-PHENYSALICYLIDENEIMINATO)-TRIPHENYLPHOSPHINEOXORHENIUM(V) AND CHLORO(8-OXYQUINOLINE) [(2-OXYMETHYLINE-6-HYDROXYMETHYL)-PYRIDINE]OXORHENIUM(V)

Abstract The reaction of the complex [ReOCl2(HL)(PPh3)] (1; H2L = 2,6-bis(hydroxymethyl)pyridine), in which HL− acts as a bidentate monoanionic N,O−-donor ligand, with the potentially bidentate N,O−-donor ligands N-phenylsalicylideneimine (PhsalH) and 8-hydroxyquinoline (oxineH) in ethanol led to the substitution of the chelate HL− to produce trans-[ReOCl2(Phsal)(PPh3)] (2) and trans-[ReOCl2(oxine)(PPh3)] (4). In benzene the mixed bis(bidentate) ligand complexes [ReOCl(Phsal)(HL)] (3) and [ReOCl(oxine)(HL)] (5) were isolated. Complex 1 also reacts with a molar excess of PhsalH and oxineH(NOH) in ethanol to form ReOCl(NO)2. All the complexes were characterized by various physical techniques, including IR and NMR. X-ray structures of 2 (C31H25Cl2NO2PRe) and 5 (C16H14ClN2O4Re) were determined. Crystals of 2 are triclinic, P 1, a = 8.813(4), b = 10.200(4), c = 16.913(7) A, α = 84.90(3), β = 80.81(3), γ = 67.44(3)°. Z = 2; those of 5 are monoclinic, P21/c, a = 14.091(2), b = 8.171(2), c = 15.227(2) A, β = 115....