title: Electronic and Molecular Structures of Pentaammineruthenium Pyridine and Benzonitrile Complexes as a Function of Oxidation State.
abstract: The structural characterization of both Ru(II) and Ru(III) compounds containing Ru(NH(3))(5)(2+/3+) with pyridine or benzonitrile as the sixth ligand (L) is described. Crystal data for L = pyridine, [(NH(3))(5)Ru(NC(5)H(5))](SO(3)CF(3))(2) (1): orthorhombic space group Pbcn, Z = 4, a = 13.096(2) Å, b = 11.541(2) Å, c = 13.179(2) Å. For [(NH(3))(5)Ru(NC(5)H(5))]Cl(3).1.4H(2)O (2): orthorhombic space group Pnma, Z = 4, a = 22.667(12) Å, b = 7.095(2) Å, c = 10.097(8) Å. For L = benzonitrile, [(NH(3))(5)Ru(NCC(6)H(5))](SO(3)CF(3))(2) (3): monoclinic space group P2(1)/n, Z = 4, a = 9.561(1) Å, b = 18.424(4) Å, c = 12.181(1) Å, beta = 95.73(1) degrees. For [(NH(3))(5)Ru(NCC(6)H(5))](S(2)O(6))(3/2).2H(2)O (4): triclinic space group P&onemacr;, Z = 2, a = 7.8947(6) Å, b = 11.517(2) Å, c = 11.630(1) Å, alpha = 99.61(1) degrees, beta = 97.275(8) degrees, gamma = 102.25(1) degrees. The Ru(II)-N(L) and Ru(III)-N(L) distances are respectively 2.058(8) and 2.077(10) Å for L = pyridine and 1.945(5) and 2.025(4) Å for L = benzonitrile. The new data yield a comprehensive set of structural parameters for modeling and interpreting electron transfer barriers and for investigating the dependence of metal-ligand coupling on d(M)(-)(N), for which the results of INDO calculations are also reported here.
authors.affiliation: Chemistry Department, Brookhaven National Laboratory, P.O. Box 5000, Upton, New York 11973-5000.
authors.forename: Yeung-gyo K.
authors.lastname: Shin Yg
authors.forename: David J.
authors.initials: DJ
authors.lastname: Szalda
authors.forename: Bruce S.
authors.initials: BS
authors.lastname: Brunschwig
authors.forename: Carol
authors.initials: C
authors.lastname: Creutz
authors.forename: Norman
authors.initials: N
authors.lastname: Sutin