Spectroscopic Identification of an FeIII Center, not FeIV, in the Crystalline Sc-O-Fe Adduct Derived from [FeIV(O)(TMC)]2+

Jai Prakash; Gregory T. Rohde; Katlyn K. Meier; Andrew J. Jasniewski; Katherine M. Van Heuvelen; Eckard Münck; Lawrence Que

doi:10.1021/jacs.5b00535

Spectroscopic Identification of an Fe^III Center, not Fe^IV, in the Crystalline Sc-O-Fe Adduct Derived from [Fe^IV(O)(TMC)]²⁺

Jai Prakash, Gregory T. Rohde, Katlyn K. Meier, Andrew J. Jasniewski, Katherine M. Van Heuvelen, Eckard Münck, Lawrence Que

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

52 Scopus citations

Abstract

The apparent Sc³⁺ adduct of [Fe^IV(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 [Fe^II(TMC)]²⁺. Thus, 1 is best described as a Sc^III-O-Fe^III 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.

Original language	English (US)
Pages (from-to)	3478-3481
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	137
Issue number	10
DOIs	https://doi.org/10.1021/jacs.5b00535
State	Published - Mar 18 2015

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© 2015 American Chemical Society.

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title = "Spectroscopic Identification of an FeIII Center, not FeIV, in the Crystalline Sc-O-Fe Adduct Derived from [FeIV(O)(TMC)]2+",

abstract = "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 M{\"o}ssbauer 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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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

PY - 2015/3/18

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