title: Regiospecific Oximato Coordination at the Oxygen Site: Ligand Design and Low-Spin Mn(II) and Fe(II/III) Species.
abstract: The (pyridylazo)oxime ligand (C(5)H(4)N)N=NC(=NOH)C(6)H(4)R(p), HRL (R = H, Me), has been synthesized with the objective of promoting the very rare mononuclear oximato-O coordination. The synthesis involves hydrazone nitrosation. HRL reacts with M(ClO(4))(2).6H(2)O, affording [M(RL)(2)] (M = Mn, Fe), and X-ray structure determinations have indeed revealed the presence of the desired oximato-O coordination mode in the distorted octahedral MN(4)O(2) sphere characterized by a 2-fold axis of symmetry relating the two tridentate ligands, all chelate rings being five-membered. The M-N and M-O distances are relatively short (1.84-1.99 Å), consistent with spin-pairing (M = Mn, S = (1)/(2); M = Fe, S = 0). The M-N bond length trend, Mn(II) > Fe(II), is in accord with the larger radius of the low-spin Mn(II) atom. The M-O length order is, however, Mn(II) < Fe(II). This reversal occurs because of the rigidity of the ligand skeleton. Significant M-azo back-bonding is present (N=N length approximately 1.30 Å). [Mn(RL)(2)] displays hyperfine-split axial EPR spectra (g( parallel) approximately 1.98, g( perpendicular) approximately 2.06, A( parallel) approximately 170 G, A( perpendicular) approximately 65 G) in frozen solution as well as in polycrystalline [Fe(RL)(2)] lattices. The quasireversible Fe(III)/Fe(II) couple of [Fe(RL)(2)] has E(1/2) approximately 0.7 V. The oxidized complex [Fe(RL)(2)]PF(6) has been electrosynthesized. It is low-spin (S = (1)/(2)) and displays axial EPR spectra (g( parallel) approximately 1.98, g( perpendicular) approximately 2.14) in frozen solution. The Mn(II) --> Mn(III) oxidation ( approximately 1.0 V) in [Mn(RL)(2)] is irreversible. Crystal data for [Mn(HL)(2)].CH(2)Cl(2): crystal system monoclinic, space group I2/a, a = 14.142(7) Å, b = 10.721(7) Å, c = 16.933(10) Å, beta = 93.01(4) degrees, Z = 4. Crystal data for [Fe(HL)(2)].CH(2)Cl(2): crystal system monoclinic, space group I2/a, a = 14.254(6) Å, b = 10.742(6) Å, c = 16.719(8) Å, beta = 92.35(4) degrees, Z = 4.
authors.affiliation: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Calcutta 700 032, India.
authors.forename: Sanjib
authors.initials: S
authors.lastname: Ganguly
authors.forename: Soma
authors.initials: S
authors.lastname: Karmakar
authors.forename: Chandan Kumar
authors.initials: CK
authors.lastname: Pal
authors.forename: Animesh
authors.initials: A
authors.lastname: Chakravorty