L-Edge X-ray Absorption Spectroscopic Investigation of {FeNO}6: Delocalization vs Antiferromagnetic Coupling

Yan, James J.; Gonzales, Margarita A.; Mascharak, Pradip K.; Hedman, Britt; Hodgson, Keith O.; Solomon, Edward I.

doi:10.1021/jacs.6b11260

Title: L-Edge X-ray Absorption Spectroscopic Investigation of {FeNO}⁶: Delocalization vs Antiferromagnetic Coupling

Journal Article · Thu Dec 22 00:00:00 EST 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b11260· OSTI ID:1361056

^[1]; Gonzales, Margarita A. ^[2];

^[3]; Hedman, Britt ^[4]; Hodgson, Keith O. ^[5]; Solomon, Edward I. ^[5]

Stanford Univ., CA (United States). Dept. of Chemistry
Foothill College, Los Altos Hills, CA (United States). Dept. of Chemistry
Univ. of California, Santa Cruz, CA (United States). Dept. of Chemistry and Biochemistry
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Stanford Univ., CA (United States). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

NO is a classic non-innocent ligand, and iron nitrosyls can have different electronic structure descriptions depending on their spin state and coordination environment. These highly covalent ligands are found in metalloproteins and are also used as models for Fe–O₂ systems. Here, this study utilizes iron L-edge X-ray absorption spectroscopy (XAS), interpreted using a valence bond configuration interaction multiplet model, to directly experimentally probe the electronic structure of the S = 0 {FeNO}⁶ compound [Fe(PaPy₃)NO]²⁺ (PaPy₃ = N,N-bis(2-pyridylmethyl)amine-N-ethyl-2-pyridine-2-carboxamide) and the S = 0 [Fe(PaPy₃)CO]⁺ reference compound. This method allows separation of the σ-donation and π-acceptor interactions of the ligand through ligand-to-metal and metal-to-ligand charge-transfer mixing pathways. The analysis shows that the {FeNO}⁶ electronic structure is best described as Fe^III–NO(neutral), with no localized electron in an NO π* orbital or electron hole in an Fe dπ orbital. This delocalization comes from the large energy gap between the Fe–NO π-bonding and antibonding molecular orbitals relative to the exchange interactions between electrons in these orbitals. This study demonstrates the utility of L-edge XAS in experimentally defining highly delocalized electronic structures.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH); National Science Foundation (NSF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-76SF00515; CHE-0957251; CHE-1360046; P41GM103393; R01GM040392

OSTI ID:: 1361056

Journal Information:: Journal of the American Chemical Society, Vol. 139, Issue 3; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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A mononuclear nonheme {FeNO} ⁶ complex: synthesis and structural and spectroscopic characterization Hong, Seungwoo; Yan, James J.; Karmalkar, Deepika G. Chemical Science, Vol. 9, Issue 34 https://doi.org/10.1039/c8sc01962b	journal	January 2018
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