A series of peroxomanganese(III) complexes supported by tetradentate aminopyridyl ligands: detailed spectroscopic and computational studies.
A set of four [Mn(II)(L(7)py(2)(R))](2+) complexes, supported by the tetradentate 1,4-bis(2-pyridylmethyl)-1,4-diazepane ligand and derivatives with pyridine substituents in the 5 (R = Br) and 6 positions (R = Me and MeO), are reported. X-ray crystal structures of these complexes all show the L(7)py(2)(R) ligands bound to give a trans complex. Treatment of these Mn(II) precursors with either H(2)O(2)/Et(3)N or KO(2) in MeCN at -40 degrees C results in the formation of peroxomanganese complexes [Mn(III)(O(2))(L(7)py(2)(R))](+) differing only in the identity of the pyridine ring substituent. The electronic structures of two of these complexes, [Mn(III)(O(2))(L(7)py(2)(H))](+) and [Mn(III)(O(2))(L(7)py(2)(Me))](+), were examined in detail using electronic absorption, low-temperature magnetic circular dichroism (MCD) and variable-temperature variable-field (VTVH) MCD spectroscopies to determine ground-state zero-field splitting (ZFS) parameters and electronic transition energies, intensities, and polarizations. DFT and TD-DFT computations were used to validate the structures of [Mn(III)(O(2))(L(7)py(2)(H))](+) and [Mn(III)(O(2))(L(7)py(2)(Me))](+), further corroborating their assignment as peroxomanganese(III) species. While these complexes exhibit similar ZFS parameters, their low-temperature MCD spectra reveal significant shifts in electronic transition energies that are correlated to differences in Mn-O(2) interactions among these complexes. Taken together, these results indicate that, while the [Mn(III)(O(2))(L(7)py(2)(H))](+) complex exhibits symmetric Mn-O(peroxo) bond lengths, consistent with a side-on bound peroxo ligand, the peroxo ligand of the [Mn(III)(O(2))(L(7)py(2)(Me))](+) complex is bound in a more end-on fashion, with asymmetric Mn-O(peroxo) distances. This difference in binding mode is rationalized in terms of the greater electron-donating abilities of the methyl-appended pyridines and suggests a simple way to modulate Mn(III)-O(2) bonding through ligand perturbations.
Department of Chemistry and Center for Environmentally Beneficial Catalysis, University of Kansas, Lawrence, Kansas 66045, USA.
Robert A
RA
Geiger
Swarup
S
Chattopadhyay
Victor W
VW
Day
Timothy A
TA
Jackson
D001381:Azepines / Q000737:chemistry; D003198:Computer Simulation; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D017895:Manganese Compounds / Q000737:chemistry*; D013058:Mass Spectrometry; D008958:Models, Molecular; D011725:Pyridines / Q000737:chemistry*; D011789:Quantum Theory
C545228:1,4-diazepane; D001381:Azepines; D017895:Manganese Compounds; D011725:Pyridines