Axial ligand substituted nonheme FeIV=O complexes: Observation of near-UV LMCT bands and Fe=O Raman vibrations

Chivukula V. Sastri; Mi Joo Park; Takehiro Ohta; Timothy A. Jackson; Audria Stubna; Mi Sook Seo; Jimin Lee; Jinheung Kim; Teizo Kitagawa; Eckard Münck; Lawrence Que; Wonwoo Nam

doi:10.1021/ja0540573

Axial ligand substituted nonheme Fe^IV=O complexes: Observation of near-UV LMCT bands and Fe=O Raman vibrations

Chivukula V. Sastri
, Mi Joo Park
, Takehiro Ohta
, Timothy A. Jackson
, Audria Stubna
, Mi Sook Seo
, Jimin Lee
, Jinheung Kim
, Teizo Kitagawa
, Eckard Münck
, Lawrence Que
, Wonwoo Nam

Department of Chemistry & Nanoscience

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

146 Scopus citations

Abstract

Axial ligand substitution of a mononuclear nonheme oxoiron(IV) complex, [Fe_IV(O)(TMC)(NCCH₃)]²⁺ (1) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), leads to the formation of new Fe_IV=O species with relatively intense electronic absorption features in the near-UV region. The presence of these near-UV features allowed us to make the first observation of Fe=O vibrations of S = 1 mononuclear nonheme oxoiron(IV) complexes by resonance Raman spectroscopy. We have also demonstrated that the reactivity of nonheme oxoiron(IV) intermediates is markedly influenced by the axial ligands.

Original language	English
Pages (from-to)	12494-12495
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	127
Issue number	36
DOIs	https://doi.org/10.1021/ja0540573
State	Published - 14 Sep 2005

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title = "Axial ligand substituted nonheme FeIV=O complexes: Observation of near-UV LMCT bands and Fe=O Raman vibrations",

abstract = "Axial ligand substitution of a mononuclear nonheme oxoiron(IV) complex, [FeIV(O)(TMC)(NCCH3)]2+ (1) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), leads to the formation of new FeIV=O species with relatively intense electronic absorption features in the near-UV region. The presence of these near-UV features allowed us to make the first observation of Fe=O vibrations of S = 1 mononuclear nonheme oxoiron(IV) complexes by resonance Raman spectroscopy. We have also demonstrated that the reactivity of nonheme oxoiron(IV) intermediates is markedly influenced by the axial ligands.",

author = "Sastri, \{Chivukula V.\} and Park, \{Mi Joo\} and Takehiro Ohta and Jackson, \{Timothy A.\} and Audria Stubna and Seo, \{Mi Sook\} and Jimin Lee and Jinheung Kim and Teizo Kitagawa and Eckard M{\"u}nck and Lawrence Que and Wonwoo Nam",

year = "2005",

month = sep,

day = "14",

doi = "10.1021/ja0540573",

language = "English",

volume = "127",

pages = "12494--12495",

journal = "Journal of the American Chemical Society",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Axial ligand substituted nonheme FeIV=O complexes

T2 - Observation of near-UV LMCT bands and Fe=O Raman vibrations

AU - Sastri, Chivukula V.

AU - Park, Mi Joo

AU - Ohta, Takehiro

AU - Jackson, Timothy A.

AU - Stubna, Audria

AU - Seo, Mi Sook

AU - Lee, Jimin

AU - Kim, Jinheung

AU - Kitagawa, Teizo

AU - Münck, Eckard

AU - Que, Lawrence

AU - Nam, Wonwoo

PY - 2005/9/14

Y1 - 2005/9/14

N2 - Axial ligand substitution of a mononuclear nonheme oxoiron(IV) complex, [FeIV(O)(TMC)(NCCH3)]2+ (1) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), leads to the formation of new FeIV=O species with relatively intense electronic absorption features in the near-UV region. The presence of these near-UV features allowed us to make the first observation of Fe=O vibrations of S = 1 mononuclear nonheme oxoiron(IV) complexes by resonance Raman spectroscopy. We have also demonstrated that the reactivity of nonheme oxoiron(IV) intermediates is markedly influenced by the axial ligands.

AB - Axial ligand substitution of a mononuclear nonheme oxoiron(IV) complex, [FeIV(O)(TMC)(NCCH3)]2+ (1) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), leads to the formation of new FeIV=O species with relatively intense electronic absorption features in the near-UV region. The presence of these near-UV features allowed us to make the first observation of Fe=O vibrations of S = 1 mononuclear nonheme oxoiron(IV) complexes by resonance Raman spectroscopy. We have also demonstrated that the reactivity of nonheme oxoiron(IV) intermediates is markedly influenced by the axial ligands.

UR - https://www.scopus.com/pages/publications/24744461128

U2 - 10.1021/ja0540573

DO - 10.1021/ja0540573

M3 - Article

C2 - 16144389

AN - SCOPUS:24744461128

SN - 0002-7863

VL - 127

SP - 12494

EP - 12495

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 36

ER -

Axial ligand substituted nonheme FeIV=O complexes: Observation of near-UV LMCT bands and Fe=O Raman vibrations

Abstract

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Axial ligand substituted nonheme Fe^IV=O complexes: Observation of near-UV LMCT bands and Fe=O Raman vibrations