TY - JOUR
T1 - Spectroscopic Identification of an FeIII Center, not FeIV, in the Crystalline Sc-O-Fe Adduct Derived from [FeIV(O)(TMC)]2+
AU - Prakash, Jai
AU - Rohde, Gregory T.
AU - Meier, Katlyn K.
AU - Jasniewski, Andrew J.
AU - Van Heuvelen, Katherine M.
AU - Münck, Eckard
AU - Que, Lawrence
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/3/18
Y1 - 2015/3/18
N2 - The apparent Sc3+ adduct of [FeIV(O)(TMC)]2+ (1, TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) has been synthesized in amounts sufficient to allow its characterization by various spectroscopic techniques. Contrary to the earlier assignment of a +4 oxidation state for the iron center of 1, we establish that 1 has a high-spin iron(III) center based on its Mössbauer and EPR spectra and its quantitative reduction by 1 equiv of ferrocene to [FeII(TMC)]2+. Thus, 1 is best described as a ScIII-O-FeIII complex, in agreement with previous DFT calculations (Swart, M. Chem. Commun. 2013, 49, 6650.). These results shed light on the interaction of Lewis acids with high-valent metal-oxo species.
AB - The apparent Sc3+ adduct of [FeIV(O)(TMC)]2+ (1, TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) has been synthesized in amounts sufficient to allow its characterization by various spectroscopic techniques. Contrary to the earlier assignment of a +4 oxidation state for the iron center of 1, we establish that 1 has a high-spin iron(III) center based on its Mössbauer and EPR spectra and its quantitative reduction by 1 equiv of ferrocene to [FeII(TMC)]2+. Thus, 1 is best described as a ScIII-O-FeIII complex, in agreement with previous DFT calculations (Swart, M. Chem. Commun. 2013, 49, 6650.). These results shed light on the interaction of Lewis acids with high-valent metal-oxo species.
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U2 - 10.1021/jacs.5b00535
DO - 10.1021/jacs.5b00535
M3 - Article
C2 - 25743366
AN - SCOPUS:84925431405
SN - 0002-7863
VL - 137
SP - 3478
EP - 3481
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 10
ER -