skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: X-ray Absorption Spectroscopy as a Probe of Ligand Noninnocence in Metallocorroles: The Case of Copper Corroles

Abstract

The question of ligand noninnocence in Cu corroles has long been a topic of discussion. This work introduces a Cu K-edge X-ray absorption spectroscopy (XAS) study, which allows a direct probe of the metal oxidation state, of three Cu corroles, Cu[TPC], Cu[Br8TPC], and Cu[(CF3)8TPC] (TPC = meso-triphenylcorrole), and the analogous Cu(II) porphyrins, Cu[TPP], Cu[Br8TPP], and Cu[(CF3)8TPP] (TPP = meso-tetraphenylporphyrin). The Cu K rising-edges of the Cu corroles were found to be about 0–1 eV upshifted relative to the analogous porphyrins, which is substantially lower than the 1–2 eV shifts typically exhibited by authentic Cu(II)/Cu(III) model complex pairs. In an unusual twist, the Cu K pre-edge regions of both the Cu corroles and the Cu porphyrins exhibit two peaks split by 0.8–1.3 eV. Based on time-dependent density functional theory calculations, the lower- and higher-energy peaks were assigned to a Cu 1s → 3d$$_{x^{2}–y^{2}}$$ transition and a Cu 1s → corrole/porphyrin π* transition, respectively. From the Cu(II) porphyrins to the corresponding Cu corroles, the energy of the Cu 1s → 3d$$_{x^{2}–y^{2}}$$ transition peak was found to upshift by 0.6–0.8 eV. This shift is approximately half that observed between Cu(II) to Cu(III) states for well-defined complexes. The Cu K-edge XAS spectra thus show that although the metal sites in the Cu corroles are more oxidized relative to those in their Cu(II) porphyrin analogues, they are not oxidized to the Cu(III) level, consistent with the notion of a noninnocent corrole. The relative importance of σ-donation versus corrole π-radical character is discussed.

Authors:
 [1];  [2];  [3];  [3]; ORCiD logo [2]; ORCiD logo [3]
  1. Stanford Univ., CA (United States)
  2. Arctic Univ. of Norway, Tromsø (Norway)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)
OSTI Identifier:
1532490
Grant/Contract Number:  
AC02-76SF00515; 231086; 262229; R01DK031450
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 58; Journal Issue: 10; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lim, Hyeongtaek, Thomas, Kolle E., Hedman, Britt, Hodgson, Keith O., Ghosh, Abhik, and Solomon, Edward I.. X-ray Absorption Spectroscopy as a Probe of Ligand Noninnocence in Metallocorroles: The Case of Copper Corroles. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.inorgchem.9b00128.
Lim, Hyeongtaek, Thomas, Kolle E., Hedman, Britt, Hodgson, Keith O., Ghosh, Abhik, & Solomon, Edward I.. X-ray Absorption Spectroscopy as a Probe of Ligand Noninnocence in Metallocorroles: The Case of Copper Corroles. United States. https://doi.org/10.1021/acs.inorgchem.9b00128
Lim, Hyeongtaek, Thomas, Kolle E., Hedman, Britt, Hodgson, Keith O., Ghosh, Abhik, and Solomon, Edward I.. Thu . "X-ray Absorption Spectroscopy as a Probe of Ligand Noninnocence in Metallocorroles: The Case of Copper Corroles". United States. https://doi.org/10.1021/acs.inorgchem.9b00128. https://www.osti.gov/servlets/purl/1532490.
@article{osti_1532490,
title = {X-ray Absorption Spectroscopy as a Probe of Ligand Noninnocence in Metallocorroles: The Case of Copper Corroles},
author = {Lim, Hyeongtaek and Thomas, Kolle E. and Hedman, Britt and Hodgson, Keith O. and Ghosh, Abhik and Solomon, Edward I.},
abstractNote = {The question of ligand noninnocence in Cu corroles has long been a topic of discussion. This work introduces a Cu K-edge X-ray absorption spectroscopy (XAS) study, which allows a direct probe of the metal oxidation state, of three Cu corroles, Cu[TPC], Cu[Br8TPC], and Cu[(CF3)8TPC] (TPC = meso-triphenylcorrole), and the analogous Cu(II) porphyrins, Cu[TPP], Cu[Br8TPP], and Cu[(CF3)8TPP] (TPP = meso-tetraphenylporphyrin). The Cu K rising-edges of the Cu corroles were found to be about 0–1 eV upshifted relative to the analogous porphyrins, which is substantially lower than the 1–2 eV shifts typically exhibited by authentic Cu(II)/Cu(III) model complex pairs. In an unusual twist, the Cu K pre-edge regions of both the Cu corroles and the Cu porphyrins exhibit two peaks split by 0.8–1.3 eV. Based on time-dependent density functional theory calculations, the lower- and higher-energy peaks were assigned to a Cu 1s → 3d$_{x^{2}–y^{2}}$ transition and a Cu 1s → corrole/porphyrin π* transition, respectively. From the Cu(II) porphyrins to the corresponding Cu corroles, the energy of the Cu 1s → 3d$_{x^{2}–y^{2}}$ transition peak was found to upshift by 0.6–0.8 eV. This shift is approximately half that observed between Cu(II) to Cu(III) states for well-defined complexes. The Cu K-edge XAS spectra thus show that although the metal sites in the Cu corroles are more oxidized relative to those in their Cu(II) porphyrin analogues, they are not oxidized to the Cu(III) level, consistent with the notion of a noninnocent corrole. The relative importance of σ-donation versus corrole π-radical character is discussed.},
doi = {10.1021/acs.inorgchem.9b00128},
journal = {Inorganic Chemistry},
number = 10,
volume = 58,
place = {United States},
year = {2019},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

The Structural Chemistry of Metallocorroles: Combined X-ray Crystallography and Quantum Chemistry Studies Afford Unique Insights
journal, March 2012

  • Thomas, Kolle E.; Alemayehu, Abraham B.; Conradie, Jeanet
  • Accounts of Chemical Research, Vol. 45, Issue 8
  • DOI: 10.1021/ar200292d

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials
journal, October 2017

  • Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.
  • Chemistry - A European Journal, Vol. 23, Issue 60
  • DOI: 10.1002/chem.201702621

Cryptic noninnocence: FeNO corroles in a new light
journal, January 2015

  • Vazquez-Lima, Hugo; Norheim, Hans-Kristian; Einrem, Rune F.
  • Dalton Transactions, Vol. 44, Issue 22
  • DOI: 10.1039/C5DT01495F

Ligand noninnocence in FeNO corroles: insights from β-octabromocorrole complexes
journal, January 2016

  • Norheim, Hans-Kristian; Capar, Jan; Einrem, Rune F.
  • Dalton Transactions, Vol. 45, Issue 2
  • DOI: 10.1039/C5DT03947A

Wolves in Sheep's Clothing: μ-Oxo-Diiron Corroles Revisited
journal, June 2016

  • Ganguly, Sumit; Vazquez-Lima, Hugo; Ghosh, Abhik
  • Chemistry - A European Journal, Vol. 22, Issue 30
  • DOI: 10.1002/chem.201601062

Electronic Structure of Copper Corroles
journal, January 2016

  • Lemon, Christopher M.; Huynh, Michael; Maher, Andrew G.
  • Angewandte Chemie International Edition, Vol. 55, Issue 6
  • DOI: 10.1002/anie.201509099

Nickel and Copper Corroles: Well-Known Complexes in a New Light
journal, March 1997

  • Will, Stefan; Lex, Johann; Vogel, Emanuel
  • Angewandte Chemie International Edition in English, Vol. 36, Issue 4
  • DOI: 10.1002/anie.199703571

X-ray Structure and Variable Temperature NMR Spectra of [ m eso -Triarylcorrolato]copper(III)
journal, July 2003

  • Brückner, Christian; Briñas, Raymond P.; Krause Bauer, Jeanette A.
  • Inorganic Chemistry, Vol. 42, Issue 15
  • DOI: 10.1021/ic034080u

β-Octafluorocorroles
journal, December 2003

  • Steene, Erik; Dey, Abhishek; Ghosh, Abhik
  • Journal of the American Chemical Society, Vol. 125, Issue 52
  • DOI: 10.1021/ja021158h

Electronic Structures and Reactivities of Corrole−Copper Complexes
journal, April 2004

  • Luobeznova, Inna; Simkhovich, Liliya; Goldberg, Israel
  • European Journal of Inorganic Chemistry, Vol. 2004, Issue 8
  • DOI: 10.1002/ejic.200300806

Revisiting the Electronic Ground State of Copper Corroles
journal, January 2007

  • Bröring, Martin; Brégier, Frédérique; Cónsul Tejero, Esther
  • Angewandte Chemie International Edition, Vol. 46, Issue 3
  • DOI: 10.1002/anie.200603676

Copper Corroles: the Question of Noninnocence
journal, November 2010

  • Pierloot, Kristine; Zhao, Hailiang; Vancoillie, Steven
  • Inorganic Chemistry, Vol. 49, Issue 22
  • DOI: 10.1021/ic100866z

Ligand Noninnocence in Coinage Metal Corroles: A Silver Knife-Edge
journal, September 2015

  • Thomas, Kolle E.; Vazquez-Lima, Hugo; Fang, Yuanyuan
  • Chemistry - A European Journal, Vol. 21, Issue 47
  • DOI: 10.1002/chem.201502150

Copper β-Octakis(trifluoromethyl)corroles: New Paradigms for Ligand Substituent Effects in Transition Metal Complexes
journal, November 2008

  • Thomas, Kolle Ekaney; Wasbotten, Ingar H.; Ghosh, Abhik
  • Inorganic Chemistry, Vol. 47, Issue 22
  • DOI: 10.1021/ic801101k

Platinum corroles
journal, January 2014

  • Alemayehu, Abraham B.; Vazquez-Lima, Hugo; Beavers, Christine M.
  • Chem. Commun., Vol. 50, Issue 76
  • DOI: 10.1039/C4CC02548B

Substituent effects on metallocorrole spectra: insights from chromium-oxo and molybdenum-oxo triarylcorroles
journal, November 2011

  • Johansen, Inge; Norheim, Hans-Kristian; Larsen, Simon
  • Journal of Porphyrins and Phthalocyanines, Vol. 15, Issue 11n12
  • DOI: 10.1142/S1088424611004270

Stepwise Deoxygenation of Nitrite as a Route to Two Families of Ruthenium Corroles: Group 8 Periodic Trends and Relativistic Effects
journal, April 2017


Oxidative Metalation as a Route to Size-Mismatched Macrocyclic Complexes: Osmium Corroles
journal, October 2014

  • Alemayehu, Abraham B.; Gagnon, Kevin J.; Terner, James
  • Angewandte Chemie International Edition, Vol. 53, Issue 52
  • DOI: 10.1002/anie.201405890

Synthesis and Molecular Structure of 99 Tc Corroles
journal, November 2016

  • Einrem, Rune F.; Braband, Henrik; Fox, Thomas
  • Chemistry - A European Journal, Vol. 22, Issue 52
  • DOI: 10.1002/chem.201605015

Metal-Ligand Misfits: Facile Access to Rhenium-Oxo Corroles by Oxidative Metalation
journal, December 2015

  • Einrem, Rune F.; Gagnon, Kevin J.; Alemayehu, Abraham B.
  • Chemistry - A European Journal, Vol. 22, Issue 2
  • DOI: 10.1002/chem.201504307

Gold corroles
journal, February 2011

  • Alemayehu, Abraham B.; Ghosh, Abhik
  • Journal of Porphyrins and Phthalocyanines, Vol. 15, Issue 02
  • DOI: 10.1142/S1088424611003045

Gold(I) and Gold(III) Corroles
journal, October 2011

  • Rabinovich, Elena; Goldberg, Israel; Gross, Zeev
  • Chemistry - A European Journal, Vol. 17, Issue 44
  • DOI: 10.1002/chem.201102348

Synthesis and Molecular Structure of Gold Triarylcorroles
journal, December 2011

  • Thomas, Kolle E.; Alemayehu, Abraham B.; Conradie, Jeanet
  • Inorganic Chemistry, Vol. 50, Issue 24
  • DOI: 10.1021/ic202023r

Relativistic effects in metallocorroles: comparison of molybdenum and tungsten biscorroles
journal, January 2017

  • Alemayehu, Abraham B.; Vazquez-Lima, Hugo; McCormick, Laura J.
  • Chemical Communications, Vol. 53, Issue 43
  • DOI: 10.1039/C7CC01549F

Tungsten Biscorroles: New Chiral Sandwich Compounds
journal, April 2016

  • Alemayehu, Abraham B.; Vazquez-Lima, Hugo; Gagnon, Kevin J.
  • Chemistry - A European Journal, Vol. 22, Issue 20
  • DOI: 10.1002/chem.201504848

Copper Corroles Are Inherently Saddled
journal, August 2009

  • Alemayehu, Abraham B.; Gonzalez, Emmanuel; Hansen, Lars Kristian
  • Inorganic Chemistry, Vol. 48, Issue 16
  • DOI: 10.1021/ic900744v

Nonplanar, Noninnocent, and Chiral: A Strongly Saddled Metallocorrole
journal, September 2010

  • Alemayehu, Abraham B.; Hansen, Lars Kristian; Ghosh, Abhik
  • Inorganic Chemistry, Vol. 49, Issue 17
  • DOI: 10.1021/ic1008736

A Metallocorrole with Orthogonal Pyrrole Rings
journal, March 2011

  • Thomas, Kolle E.; Conradie, Jeanet; Hansen, Lars K.
  • European Journal of Inorganic Chemistry, Vol. 2011, Issue 12
  • DOI: 10.1002/ejic.201100170

Undecaphenylcorroles
journal, September 2012

  • Berg, Steffen; Thomas, Kolle E.; Beavers, Christine M.
  • Inorganic Chemistry, Vol. 51, Issue 18
  • DOI: 10.1021/ic301388e

Halterman Corroles and Their Use as a Probe of the Conformational Dynamics of the Inherently Chiral Copper Corrole Chromophore
journal, March 2018


Synthesis and Molecular Structure of a Copper Octaiodocorrole
journal, May 2018


Ligand Noninnocence in Silver Corroles: A XANES Investigation: Ligand Noninnocence in Silver Corroles: A XANES Investigation
journal, June 2016

  • Sarangi, Ritimukta; Giles, Logan J.; Thomas, Kolle E.
  • European Journal of Inorganic Chemistry, Vol. 2016, Issue 20
  • DOI: 10.1002/ejic.201600413

Spectroelectrochemical and ESR studies of highly substituted copper corroles
journal, October 2004

  • Ou, Zhongping; Shao, Jianguo; Zhao, Hui
  • Journal of Porphyrins and Phthalocyanines, Vol. 08, Issue 10
  • DOI: 10.1142/S1088424604000593

Cobalt- and Rhodium-Corrole-Triphenylphosphine Complexes Revisited: The Question of a Noninnocent Corrole
journal, December 2017


Molecular Redox: Revisiting the Electronic Structures of the Group 9 Metallocorroles
journal, November 2012

  • Palmer, Joshua H.; Lancaster, Kyle M.
  • Inorganic Chemistry, Vol. 51, Issue 22
  • DOI: 10.1021/ic3018826

X-ray absorption near-edge spectroscopy in bioinorganic chemistry: Application to M–O2 systems
journal, January 2013


X-ray absorption edge determination of the oxidation state and coordination number of copper. Application to the type 3 site in Rhus vernicifera laccase and its reaction with oxygen
journal, October 1987

  • Kau, Lung Shan; Spira-Solomon, Darlene J.; Penner-Hahn, James E.
  • Journal of the American Chemical Society, Vol. 109, Issue 21
  • DOI: 10.1021/ja00255a032

A Systematic K-edge X-ray Absorption Spectroscopic Study of Cu(III) Sites
journal, June 2000

  • DuBois, Jennifer L.; Mukherjee, Pulakesh; Stack, T. D. P.
  • Journal of the American Chemical Society, Vol. 122, Issue 24
  • DOI: 10.1021/ja993134p

Prediction of Iron K-Edge Absorption Spectra Using Time-Dependent Density Functional Theory
journal, December 2008

  • DeBeer George, Serena; Petrenko, Taras; Neese, Frank
  • The Journal of Physical Chemistry A, Vol. 112, Issue 50
  • DOI: 10.1021/jp803174m

Prediction of high-valent iron K-edge absorption spectra by time-dependent Density Functional Theory
journal, January 2011

  • Chandrasekaran, P.; Stieber, S. Chantal E.; Collins, Terrence J.
  • Dalton Transactions, Vol. 40, Issue 42
  • DOI: 10.1039/c1dt11331c

Manganese K-Edge X-Ray Absorption Spectroscopy as a Probe of the Metal–Ligand Interactions in Coordination Compounds
journal, December 2011

  • Roemelt, Michael; Beckwith, Martha A.; Duboc, Carole
  • Inorganic Chemistry, Vol. 51, Issue 1
  • DOI: 10.1021/ic202229b

High-resolution molybdenum K-edge X-ray absorption spectroscopy analyzed with time-dependent density functional theory
journal, January 2013

  • Lima, Frederico A.; Bjornsson, Ragnar; Weyhermüller, Thomas
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 48
  • DOI: 10.1039/c3cp53133c

Experimental and Theoretical Investigations of the Existence of Cu II , Cu III , and Cu IV in Copper Corrolato Complexes
journal, September 2015

  • Sinha, Woormileela; Sommer, Michael G.; Deibel, Naina
  • Angewandte Chemie International Edition, Vol. 54, Issue 46
  • DOI: 10.1002/anie.201507330

Re-evaluating the Cu K pre-edge XAS transition in complexes with covalent metal–ligand interactions
journal, January 2015

  • Tomson, Neil C.; Williams, Kamille D.; Dai, Xuliang
  • Chemical Science, Vol. 6, Issue 4
  • DOI: 10.1039/C4SC03294B

Probing Cu I in homogeneous catalysis using high-energy-resolution fluorescence-detected X-ray absorption spectroscopy
journal, January 2015

  • Walroth, Richard C.; Uebler, Jacob W. H.; Lancaster, Kyle M.
  • Chemical Communications, Vol. 51, Issue 48
  • DOI: 10.1039/C5CC01827G

Spectroscopic Evidence for a 3d 10 Ground State Electronic Configuration and Ligand Field Inversion in [Cu(CF 3 ) 4 ] 1–
journal, February 2016

  • Walroth, Richard C.; Lukens, James T.; MacMillan, Samantha N.
  • Journal of the American Chemical Society, Vol. 138, Issue 6
  • DOI: 10.1021/jacs.5b10819

Electronic Structural Analysis of Copper(II)–TEMPO/ABNO Complexes Provides Evidence for Copper(I)–Oxoammonium Character
journal, September 2017

  • Walroth, Richard C.; Miles, Kelsey C.; Lukens, James T.
  • Journal of the American Chemical Society, Vol. 139, Issue 38
  • DOI: 10.1021/jacs.7b07186

X-ray Absorption Edge Spectroscopy and Computational Studies on LCuO 2 Species:  Superoxide−Cu II versus Peroxide−Cu III Bonding
journal, June 2006

  • Sarangi, Ritimukta; Aboelella, Nermeen; Fujisawa, Kiyoshi
  • Journal of the American Chemical Society, Vol. 128, Issue 25
  • DOI: 10.1021/ja0615223

Ground-State Copper(III) Stabilized by N-Confused/N-Linked Corroles: Synthesis, Characterization, and Redox Reactivity
journal, April 2018

  • Maurya, Yogesh Kumar; Noda, Katsuya; Yamasumi, Kazuhisa
  • Journal of the American Chemical Society, Vol. 140, Issue 22
  • DOI: 10.1021/jacs.8b01876

Azulicorrole
journal, April 2019


A simplified synthesis for meso-tetraphenylporphine
journal, February 1967

  • Adler, Alan D.; Longo, Frederick R.; Finarelli, John D.
  • The Journal of Organic Chemistry, Vol. 32, Issue 2
  • DOI: 10.1021/jo01288a053

Octabromotetraphenylporphyrin and its metal derivatives: Electronic structure and electrochemical properties
journal, January 1991


Fluoroalkylation of Porphyrins: A Facile Synthesis of Trifluoromethylated Porphyrins by a Palladium-Catalyzed Cross-Coupling Reaction
journal, September 2005

  • Liu, Chao; Chen, Qing-Yun
  • European Journal of Organic Chemistry, Vol. 2005, Issue 17
  • DOI: 10.1002/ejoc.200500027

Efficient Synthesis of meso-Substituted Corroles in a H 2 O−MeOH Mixture
journal, May 2006

  • Koszarna, Beata; Gryko, Daniel T.
  • The Journal of Organic Chemistry, Vol. 71, Issue 10
  • DOI: 10.1021/jo060007k

PySpline: A Modern, Cross-Platform Program for the Processing of Raw Averaged XAS Edge and EXAFS Data
conference, January 2007

  • Tenderholt, Adam; Hedman, Britt; Hodgson, Keith O.
  • X-RAY ABSORPTION FINE STRUCTURE - XAFS13: 13th International Conference, AIP Conference Proceedings
  • DOI: 10.1063/1.2644442

Chemistry with ADF
journal, January 2001

  • te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
  • Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
  • DOI: 10.1002/jcc.1056

Density-functional approximation for the correlation energy of the inhomogeneous electron gas
journal, June 1986


Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

The ORCA program system: The ORCA program system
journal, June 2011

  • Neese, Frank
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1
  • DOI: 10.1002/wcms.81

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


All-Electron Scalar Relativistic Basis Sets for Third-Row Transition Metal Atoms
journal, May 2008

  • Pantazis, Dimitrios A.; Chen, Xian-Yang; Landis, Clark R.
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 6
  • DOI: 10.1021/ct800047t

Relativistic regular two‐component Hamiltonians
journal, September 1993

  • Lenthe, E. van; Baerends, E. J.; Snijders, J. G.
  • The Journal of Chemical Physics, Vol. 99, Issue 6
  • DOI: 10.1063/1.466059

COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient
journal, January 1993


    Works referencing / citing this record:

    Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand interactions
    journal, January 2020

    • Thomas, Kolle E.; Desbois, Nicolas; Conradie, Jeanet
    • RSC Advances, Vol. 10, Issue 1
    • DOI: 10.1039/c9ra09228e