SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF SEVERAL RUTHENIUM PORPHYRIN NITROSYL COMPLEXES

The synthesis, X-ray crystal structures, and some spectroscopic and ch emical properties of the nitrosylruthenium(II) porphyrin complexes Ru( TPP)(NO)(ONO), Ru(TPP)(NO)(OH), Ru(OEP)(NO)(ONO), and Ru(OEP)(NO)(OH) (TPP = tetraphenylporphyrinato dianion; OEP = octaethylporphyrinato di anion) derived from the analogous Ru(II) carbonyl complexes are report ed. Also described are experiments which quantitatively demonstrate th at N2O is formed as a product of the synthesis scheme and that NO serv es as the principal oxidant in the transformation of N(II) to N(III). The two TPP complexes are isostructural and consist of columns of mole cules stacked along the c axis. The two OEP complexes are also isostru ctural and can be considered as layers of OEP complexes stacked along the b axis with solvent molecules situated at the cavities between lay ers. The nitrite ions are coordinated in a unidentate fashion through the oxygen atom. Crystal data for Ru(TPP)(NO)(ONO) (1): M = 789.79, sp ace group I4/m (no. 87), a = 13.6529(6) Angstrom, c = 9.7904(5) Angstr om, V = 1825.0(2) Angstrom(3), Z = 2, rho = 1.437 g cm(-3), purple bip yramid, 2 theta(max) = 50.0 degrees, R(F) = 4.87% for 86 parameters an d 838 reflections with I > 2 sigma(I). Crystal data for Ru(TPP)(NO)(OH ) (2): M = 760.79, space group I4/m (No. 87), a = 13.5423(4) Angstrom, c = 9.7150(4) Angstrom, V = 1781.7(1) Angstrom(3), Z = 2, rho = 1.418 g cm(-3), dark red plate, 2 theta(max) = 50.0 degrees, R(F) = 3.92% f or 83 parameters and 811 reflections with I > 2 sigma(I). Crystals dat a for Ru(OEP)(NO)(OH). C2H5OH (4): M = 726.91, space group P2(1) (No. 4), a = 10.8474(7) Angstrom, b = 21.002(1) Angstrom, c = 8.3646(5) Ang strom, beta = 103.571(1)degrees, V = 1852.4(2) Angstrom(3), Z = 2, rho = 1.303 g cm(-3), brown plate, 2 theta(max) = 45.0 degrees, R(F) = 6. 74% for 421 parameters and 3527 reflections with I > 2 sigma(I).