X-RAY STRUCTURE, LIGAND SUBSTITUTION, AND OTHER PROPERTIES OF TRINUCLEAR RUTHENIUM COMPLEX, [RU3(MU-3-O)(MU-C6H5COO)6(PY)3](PF6) (PY=PYRIDINE), AND X-RAY STRUCTURE OF DINUCLEAR RUTHENIUM COMPLEX, [RU2(MU-C6H5COO)4CL]

Crystal structure of an oxo-benzoate-bridged trinuclear ruthenium complex, [Ru3(mu-3-O)(mu-C6H5COO)6(py)3](PF6) (py = pyridine) (1), was determined for the first time for the complexes with a Ru3(III,III,III)(mu-3-O) core. The complex crystallizes in hexagonal space group P6(3) with a=13.619(6), c=19.204(9) angstrom, V=3085(3) angstrom3, and Z=2. The Ru ... Ru distance of 3.350(2) angstrom is similar to those of the trinuclear complexes of other metal ions, [M(III)3(mu-3-O)(mu-RCOO)6(L)3]+(L = neutral unidentate ligand). The complex in 0.1 M (n-C4H9)4NPF6-acetonitrile at 20-degrees-C shows four reversible one-electron processes at E1/2=+ 1.58, +0.71, -0.26, and - 1.54 V vs. Ag/ Ag+ (0.1 M AgClO4). It undergoes pyridine-d5 exchange with the first-order rate constant, 4.9X10(-6) s-1 at 60-degrees-C ([1] = 4.7 mM, [py-d5] = 387 mM). Small modification of the synthetic procedure of the trinuclear complex leads to the precipitation of the crystals of well-known type of dimeric ruthenium (II,III) complex, [Ru2(mu-C6H5COO)4Cl], which crystallizes in monoclinic space group C2/ c with a=21.668(10), b= 10.741(8), c= 12.797(5) angstrom, beta= 110.22(4)-degrees, V=2795(3) angstrom3, and Z=4. The crystal contains infinite zig-zag chain of ... Cl-Ru-Ru-Cl ... along c-axis with Ru-Ru-Cl of 175.5(1)-degrees, Ru-Cl-Ru of 118.1(1)-degrees, and the Ru-Ru distance of 2.290(1) angstrom.