Raman spectra and normal coordinate analyses of low-frequency vibrations of oxo-bridged manganese complexes.
The active sites of certain metalloenzymes involved in oxygen metabolism, such as manganese catalase and the oxygen-evolving complex of photosystem II, contain micro -oxo-bridged Mn clusters with ligands that include H(2)O and micro (1,3)-carboxylato bridges provided by protein side chains. In order to understand better the vibrational spectra of such clusters, the low-frequency resonance Raman spectra of a series of structurally characterized Mn-oxo model complexes were examined. The series includes complexes of the type [Mn(2)(O)(OAc)(2)(bpy)(2)(L)(2)] and [Mn(2)(O)(2)(OAc)(bpy)(2)(L)(2)], where bpy=2,2'-bipyridine, OAc=acetate and L=H(2)O or Cl(-). Complexes containing the isotopomers OAc- d(3) and D(2)O, as well as those containing both isotopomers, were also examined. Normal coordinate analyses (NCA) were performed on the various complexes using theGF matrix method. Selected vibrational modes in the 200-600 cm(-1) region were assigned based on the spectra and NCA, which identify vibrational modes arising from the metal-ligand bonds. These results will be useful in interpreting the vibrational spectra obtained from metalloproteins containing Mn-oxo complexes in their active sites.
Cua
Agnes
A
Department of Chemistry, University of California, Riverside, CA 92521-0403, USA.
Vrettos
John S
JS
de Paula
Julio C
JC
Brudvig
Gary W
GW
Bocian
David F
DF
D003460:Crystallization; D008024:Ligands; D017895:Manganese Compounds / Q000032:analysis* / Q000737:chemistry; D009942:Organometallic Compounds / Q000032:analysis* / Q000737:chemistry; D010100:Oxygen / Q000032:analysis* / Q000737:chemistry; D013059:Spectrum Analysis, Raman / Q000379:methods*; D014732:Vibration
D008024:Ligands; D017895:Manganese Compounds; D009942:Organometallic Compounds; D010100:Oxygen