Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts.
We report the synthesis, characterization, and reactivity of [LFe3(PhPz)3OMn(sPhIO)][OTf]x(3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically,57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (FeIII2FeIIMnIIvs. FeIII3MnII) influence oxygen atom transfer in tetranuclear Fe3Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.
Department of Chemistry and Chemical Engineering, California Institute of Technology; MC 127-72, Pasadena, CA, 91125, USA.
Graham
G
de Ruiter
Department of Chemistry and Chemical Engineering, California Institute of Technology; MC 127-72, Pasadena, CA, 91125, USA.
Kurtis M
KM
Carsch
Molecular Biophysics & Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
Sheraz
S
Gul
Molecular Biophysics & Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
Ruchira
R
Chatterjee
Department of Chemistry and Chemical Engineering, California Institute of Technology; MC 127-72, Pasadena, CA, 91125, USA.
Niklas B
NB
Thompson
Department of Chemistry and Chemical Engineering, California Institute of Technology; MC 127-72, Pasadena, CA, 91125, USA.
Michael K
MK
Takase
Molecular Biophysics & Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
Junko
J
Yano
Department of Chemistry and Chemical Engineering, California Institute of Technology; MC 127-72, Pasadena, CA, 91125, USA.
Theodor
0000-0002-9692-7614
T
Agapie
D018360:Crystallography, X-Ray; D004583:Electrons; D007462:Iodobenzenes / Q000737:chemistry*; D058085:Iron Compounds / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D008958:Models, Molecular; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*
D007462:Iodobenzenes; D058085:Iron Compounds; D008345:Manganese; D010100:Oxygen; C037276:iodosobenzene
C−H bond oxygenation; clusters; iodosobenzene adduct; multimetallic complexes; oxygen atom transfer