TY - JOUR
T1 - Spectroscopic and theoretical study of a mononuclear manganese(III) complex exhibiting a tetragonally compressed geometry
AU - Scheifele, Quirin
AU - Riplinger, Christoph
AU - Neese, Frank
AU - Weihe, Høgni
AU - Barra, Anne Laure
AU - Juranyi, Fanni
AU - Podlesnyak, Andrei
AU - Tregenna-Piggott, Philip L.W.
PY - 2008/1/21
Y1 - 2008/1/21
N2 - Inelastic neutron scattering and high-field electron paramagnetic resonance data are presented for [Mn(bpia)(OAc)(OCH3)](PF6), where bpia is bis(picolyl)(N-methylimidazole-2-yl)amine. Modeling of the data to the conventional fourth-order spin-Hamiltonian yielded the following parameters: D = 3.526(3) cm-1, E = 0.588(6) cm-1, B4 0 = -0.00084(7) cm-1, B42 = -0.002(2) cm-1, B44 = -0.0082(5) cm -1, gx = 1.98(1), gy = 1.952(6), and g z = 1.978(5). The complex is of particular interest given the biochemical activity and the unusual stereochemistry distinguished by a rare example of a tetragonally compressed octahedron and a pronounced angular distortion imposed by the tetradentate tripodal bpia ligand. Ligand field, density functional theory, and complete active space self-consistent field ab initio calculations are presented that aim to relate the spectroscopic data to the molecular geometry.
AB - Inelastic neutron scattering and high-field electron paramagnetic resonance data are presented for [Mn(bpia)(OAc)(OCH3)](PF6), where bpia is bis(picolyl)(N-methylimidazole-2-yl)amine. Modeling of the data to the conventional fourth-order spin-Hamiltonian yielded the following parameters: D = 3.526(3) cm-1, E = 0.588(6) cm-1, B4 0 = -0.00084(7) cm-1, B42 = -0.002(2) cm-1, B44 = -0.0082(5) cm -1, gx = 1.98(1), gy = 1.952(6), and g z = 1.978(5). The complex is of particular interest given the biochemical activity and the unusual stereochemistry distinguished by a rare example of a tetragonally compressed octahedron and a pronounced angular distortion imposed by the tetradentate tripodal bpia ligand. Ligand field, density functional theory, and complete active space self-consistent field ab initio calculations are presented that aim to relate the spectroscopic data to the molecular geometry.
UR - http://www.scopus.com/inward/record.url?scp=38949218377&partnerID=8YFLogxK
U2 - 10.1021/ic701665u
DO - 10.1021/ic701665u
M3 - Article
AN - SCOPUS:38949218377
SN - 0020-1669
VL - 47
SP - 439
EP - 447
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 2
ER -