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Title: Effect of Redox-Inactive Metal Ion–Nickel(III) Interactions on the Redox Properties and Proton-Coupled Electron Transfer Reactivity

Abstract

We report Mononuclear nickel(II) and nickel(III) complexes of a bisamidate-bisalkoxide ligand, (NMe4)2[Ni-II(HMPAB)] (1) and (NMe4)[NiIII(HMPAB)] (2), respectively, have been synthesized and characterized by various spectroscopic techniques including X-ray crystallography. The reaction of redox-inactive metal ions (Mn+ = Ca2+, Mg2+, Zn2+, Y3+, and Sc3+) with 2 resulted in 2-Mn+ adducts, which was assessed by an array of spectroscopic techniques including X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and reactivity studies. The X-ray structure of Ca2+ coordinated to Ni(III) complexes, 2Ca2+T, was determined and exhibited an average Ni-Ca distance of 3.1253 angstrom, close to the metal ions' covalent radius. XAS analysis of 2-Ca2+ and 2-Y3+ in solution further revealed an additional coordination to Ca and Y in the 2-Mn+ adducts with shortened Ni-M distances of 2.15 and 2.11 Å, respectively, implying direct bonding interactions between Ni and Lewis acids (LAs). Such a short interatomic distance between Ni(III) and M is unprecedented and was not observed before. EPR analysis of 2 and 2-Mn+ species, moreover, displayed rhombic signals with gav > 2.12 for all complexes, supporting the +III oxidation state of Ni. The NiIII/NiII redox potential of 2 and 2-Mn+ species was determined, and a plot of E1/ 2 of 2-Mn+ versusmore » pKa of [M(H2O)n]m+ exhibited a linear relationship, implying that the NiIII/NiII potential of 2 can be tuned with different redox-inactive metal ions. Reactivity studies of 2 and 2-Mn+ with different 4-X-2,6-ditert-butylphenol (4-XDTBP) and other phenol derivatives were performed, and based on kinetic studies, we propose the involvement of a proton-coupled electron transfer (PCET) pathway. Analysis of the reaction products after the reaction of 2 with 4-OMe-DTBP showed the formation of a Ni(II) complex (1a) where one of the alkoxide arms of the ligand is protonated. A pKa value of 24.2 was estimated for 1a. The reaction of 2-Mn+ species was examined with 4-OMe-DTBP, and it was observed that the k2 values of 2-Mn+ species increase by increasing the Lewis acidity of redox-inactive metal ions. However, the obtained k2 values for 2-Mn+ species are much lower compared to the k2 value for 2. Such a variation of PCET reactivity between 2 and 2-Mn+ species may be attributed to the interactions between Ni(III) and LAs. Our findings show the significance of the secondary coordination sphere effect on the PCET reactivity of Ni(III) complexes and furnish important insights into the reaction mechanism involving high-valent nickel species, which are frequently invoked as key intermediates in Ni-mediated enzymatic reactions, solar-fuel catalysis, and biomimetic/synthetic transformation reactions.« less

Authors:
 [1];  [1];  [1];  [2]; ORCiD logo [3];  [3]; ORCiD logo [4]; ORCiD logo [1]
+ Show Author Affiliations
  1. Indian Institute of Technology (IIT), New Delhi (India)
  2. Indian Association for the Cultivation of Science, Kolkata (India)
  3. Argonne National Laboratory (ANL), Lemont, IL (United States)
  4. Instituto de Ciencia de Materiales de Madrid, Madrid (Spain)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); Council of Scientific and Industrial Research (CSIR); Canadian Light Source, Inc.; Spanish Ministry of Science and Innovation (MICINN); Ramon y Cajal Fellowship
OSTI Identifier:
1970723
Grant/Contract Number:  
AC02-06CH11357; ECR/2017/002433; PID2019-111086RA-I00; 20226AT001; RYC2020-029863-I; 730872
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 61; Journal Issue: 36; 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

Kaur, Simarjeet, Bera, Moumita, Santra, Aakash, Munshi, Sandip, Sterbinsky, George E., Wu, Tianpin, Moonshiram, Dooshaye, and Paria, Sayantan. Effect of Redox-Inactive Metal Ion–Nickel(III) Interactions on the Redox Properties and Proton-Coupled Electron Transfer Reactivity. United States: N. p., 2022. Web. doi:10.1021/acs.inorgchem.2c01472.
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Kaur, Simarjeet, Bera, Moumita, Santra, Aakash, Munshi, Sandip, Sterbinsky, George E., Wu, Tianpin, Moonshiram, Dooshaye, & Paria, Sayantan. Effect of Redox-Inactive Metal Ion–Nickel(III) Interactions on the Redox Properties and Proton-Coupled Electron Transfer Reactivity. United States. https://doi.org/10.1021/acs.inorgchem.2c01472
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Kaur, Simarjeet, Bera, Moumita, Santra, Aakash, Munshi, Sandip, Sterbinsky, George E., Wu, Tianpin, Moonshiram, Dooshaye, and Paria, Sayantan. Tue . "Effect of Redox-Inactive Metal Ion–Nickel(III) Interactions on the Redox Properties and Proton-Coupled Electron Transfer Reactivity". United States. https://doi.org/10.1021/acs.inorgchem.2c01472. https://www.osti.gov/servlets/purl/1970723.
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@article{osti_1970723,
title = {Effect of Redox-Inactive Metal Ion–Nickel(III) Interactions on the Redox Properties and Proton-Coupled Electron Transfer Reactivity},
author = {Kaur, Simarjeet and Bera, Moumita and Santra, Aakash and Munshi, Sandip and Sterbinsky, George E. and Wu, Tianpin and Moonshiram, Dooshaye and Paria, Sayantan},
abstractNote = {We report Mononuclear nickel(II) and nickel(III) complexes of a bisamidate-bisalkoxide ligand, (NMe4)2[Ni-II(HMPAB)] (1) and (NMe4)[NiIII(HMPAB)] (2), respectively, have been synthesized and characterized by various spectroscopic techniques including X-ray crystallography. The reaction of redox-inactive metal ions (Mn+ = Ca2+, Mg2+, Zn2+, Y3+, and Sc3+) with 2 resulted in 2-Mn+ adducts, which was assessed by an array of spectroscopic techniques including X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and reactivity studies. The X-ray structure of Ca2+ coordinated to Ni(III) complexes, 2Ca2+T, was determined and exhibited an average Ni-Ca distance of 3.1253 angstrom, close to the metal ions' covalent radius. XAS analysis of 2-Ca2+ and 2-Y3+ in solution further revealed an additional coordination to Ca and Y in the 2-Mn+ adducts with shortened Ni-M distances of 2.15 and 2.11 Å, respectively, implying direct bonding interactions between Ni and Lewis acids (LAs). Such a short interatomic distance between Ni(III) and M is unprecedented and was not observed before. EPR analysis of 2 and 2-Mn+ species, moreover, displayed rhombic signals with gav > 2.12 for all complexes, supporting the +III oxidation state of Ni. The NiIII/NiII redox potential of 2 and 2-Mn+ species was determined, and a plot of E1/ 2 of 2-Mn+ versus pKa of [M(H2O)n]m+ exhibited a linear relationship, implying that the NiIII/NiII potential of 2 can be tuned with different redox-inactive metal ions. Reactivity studies of 2 and 2-Mn+ with different 4-X-2,6-ditert-butylphenol (4-XDTBP) and other phenol derivatives were performed, and based on kinetic studies, we propose the involvement of a proton-coupled electron transfer (PCET) pathway. Analysis of the reaction products after the reaction of 2 with 4-OMe-DTBP showed the formation of a Ni(II) complex (1a) where one of the alkoxide arms of the ligand is protonated. A pKa value of 24.2 was estimated for 1a. The reaction of 2-Mn+ species was examined with 4-OMe-DTBP, and it was observed that the k2 values of 2-Mn+ species increase by increasing the Lewis acidity of redox-inactive metal ions. However, the obtained k2 values for 2-Mn+ species are much lower compared to the k2 value for 2. Such a variation of PCET reactivity between 2 and 2-Mn+ species may be attributed to the interactions between Ni(III) and LAs. Our findings show the significance of the secondary coordination sphere effect on the PCET reactivity of Ni(III) complexes and furnish important insights into the reaction mechanism involving high-valent nickel species, which are frequently invoked as key intermediates in Ni-mediated enzymatic reactions, solar-fuel catalysis, and biomimetic/synthetic transformation reactions.},
doi = {10.1021/acs.inorgchem.2c01472},
journal = {Inorganic Chemistry},
number = 36,
volume = 61,
place = {United States},
year = {Tue Aug 30 00:00:00 EDT 2022},
month = {Tue Aug 30 00:00:00 EDT 2022}
}
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Works referenced in this record:

Metal ion-coupled electron-transfer reactions of metal-oxygen complexes
journal, May 2020

Activation of Metal Oxo and Nitrido Complexes by Lewis Acids
journal, February 2019

  • Liu, Yingying; Lau, Tai-Chu
  • Journal of the American Chemical Society, Vol. 141, Issue 9
  • DOI: 10.1021/jacs.8b13100

Calcium reconstitutes high rates of oxygen evolution in polypeptide depleted Photosystem II preparations
journal, February 1984

Structure of Sr-substituted photosystem II at 2.1 A resolution and its implications in the mechanism of water oxidation
journal, February 2013

  • Koua, F. H. M.; Umena, Y.; Kawakami, K.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 10
  • DOI: 10.1073/pnas.1219922110

Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer
journal, July 2010

  • Fukuzumi, Shunichi; Morimoto, Yuma; Kotani, Hiroaki
  • Nature Chemistry, Vol. 2, Issue 9
  • DOI: 10.1038/nchem.731

Evidence for an oxygen evolving iron–oxo–cerium intermediate in iron-catalysed water oxidation
journal, January 2015

  • Codolà, Zoel; Gómez, Laura; Kleespies, Scott T.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms6865

Valence Tautomerism in a High-Valent Manganese–Oxo Porphyrinoid Complex Induced by a Lewis Acid
journal, June 2012

  • Leeladee, Pannee; Baglia, Regina A.; Prokop, Katharine A.
  • Journal of the American Chemical Society, Vol. 134, Issue 25
  • DOI: 10.1021/ja304609n

A Mononuclear Non-Heme Manganese(IV)–Oxo Complex Binding Redox-Inactive Metal Ions
journal, January 2013

  • Chen, Junying; Lee, Yong-Min; Davis, Katherine M.
  • Journal of the American Chemical Society, Vol. 135, Issue 17
  • DOI: 10.1021/ja312113p

A Manganese(V)–Oxo Complex: Synthesis by Dioxygen Activation and Enhancement of Its Oxidizing Power by Binding Scandium Ion
journal, June 2016

  • Hong, Seungwoo; Lee, Yong-Min; Sankaralingam, Muniyandi
  • Journal of the American Chemical Society, Vol. 138, Issue 27
  • DOI: 10.1021/jacs.6b03874

Redox Reactivity of a Mononuclear Manganese-Oxo Complex Binding Calcium Ion and Other Redox-Inactive Metal Ions
journal, December 2018

  • Sankaralingam, Muniyandi; Lee, Yong-Min; Pineda-Galvan, Yuliana
  • Journal of the American Chemical Society, Vol. 141, Issue 3
  • DOI: 10.1021/jacs.8b11492

Electrochemical Properties and Reactivity Study of [MnV(O)(μ-OR–Lewis Acid)] Cores
journal, November 2021

A hexagonal planar transition-metal complex
journal, October 2019

Nickel(0)-Induced β-H Elimination of Magnesium Alkyls: Formation and Reactivity of Heterometallic Hydrides
journal, September 2020

d–d Dative Bonding Between Iron and the Alkaline‐Earth Metals Calcium, Strontium, and Barium
journal, July 2020

  • Stegner, Philipp; Färber, Christian; Oetzel, Jan
  • Angewandte Chemie International Edition, Vol. 59, Issue 34
  • DOI: 10.1002/anie.202005774

Formation and Characterization of BeFe(CO) 4 − Anion with Beryllium−Iron Bonding
journal, March 2021

  • Wang, Guanjun; Zhao, Jing; Hu, Han‐Shi
  • Angewandte Chemie International Edition, Vol. 60, Issue 17
  • DOI: 10.1002/anie.202015760

Activation of a High-Valent Manganese–Oxo Complex by a Nonmetallic Lewis Acid
journal, May 2014

  • Baglia, Regina A.; Dürr, Maximilian; Ivanović-Burmazović, Ivana
  • Inorganic Chemistry, Vol. 53, Issue 12
  • DOI: 10.1021/ic500901y

Strong Inhibition of O-Atom Transfer Reactivity for Mn IV (O)(π-Radical-Cation)(Lewis Acid) versus Mn V (O) Porphyrinoid Complexes
journal, May 2015

  • Zaragoza, Jan Paulo T.; Baglia, Regina A.; Siegler, Maxime A.
  • Journal of the American Chemical Society, Vol. 137, Issue 20
  • DOI: 10.1021/jacs.5b00875

[FeFe]- and [NiFe]-hydrogenase diversity, mechanism, and maturation
journal, June 2015

  • Peters, John W.; Schut, Gerrit J.; Boyd, Eric S.
  • Biochimica et Biophysica Acta (BBA) - Molecular Cell Research, Vol. 1853, Issue 6
  • DOI: 10.1016/j.bbamcr.2014.11.021

Single Crystal EPR Studies of the Reduced Active Site of [NiFe] Hydrogenase from Desulfovibrio vulgaris Miyazaki F
journal, January 2003

  • Foerster, Stefanie; Stein, Matthias; Brecht, Marc
  • Journal of the American Chemical Society, Vol. 125, Issue 1
  • DOI: 10.1021/ja027522u

Nickel Superoxide Dismutase Structure and Mechanism †
journal, June 2004

  • Barondeau, David P.; Kassmann, Carey J.; Bruns, Cami K.
  • Biochemistry, Vol. 43, Issue 25
  • DOI: 10.1021/bi0496081

S K-Edge X-ray Absorption Spectroscopic Investigation of the Ni-Containing Superoxide Dismutase Active Site:  New Structural Insight into the Mechanism
journal, February 2004

  • Szilagyi, Robert K.; Bryngelson, Peter A.; Maroney, Michael J.
  • Journal of the American Chemical Society, Vol. 126, Issue 10
  • DOI: 10.1021/ja039106v

Mechanism and Selectivity in Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Halides with Alkyl Halides
journal, October 2013

  • Biswas, Soumik; Weix, Daniel J.
  • Journal of the American Chemical Society, Vol. 135, Issue 43
  • DOI: 10.1021/ja407589e

Suzuki Cross-Couplings of Unactivated Secondary Alkyl Bromides and Iodides
journal, January 2004

  • Zhou, Jianrong (Steve); Fu, Gregory C.
  • Journal of the American Chemical Society, Vol. 126, Issue 5
  • DOI: 10.1021/ja039889k

Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes
journal, February 2015

NiII(TPA) as an efficient catalyst for alkane hydroxylation with m-CPBA
journal, January 2006

  • Nagataki, Takayuki; Tachi, Yoshimitsu; Itoh, Shinobu
  • Chemical Communications, Issue 38
  • DOI: 10.1039/b608311k

Ligand effects on NiII-catalysed alkane-hydroxylation with m-CPBA
journal, January 2007

  • Nagataki, Takayuki; Ishii, Kenta; Tachi, Yoshimitsu
  • Dalton Transactions, Issue 11
  • DOI: 10.1039/b615503k

Ni(II)/H2O2 Reactivity in Bis[(pyridin-2-yl)methyl]amine Tridentate Ligand System. Aromatic Hydroxylation Reaction by Bis(μ-oxo)dinickel(III) Complex
journal, April 2009

  • Kunishita, Atsushi; Doi, Yoshitaka; Kubo, Minoru
  • Inorganic Chemistry, Vol. 48, Issue 11
  • DOI: 10.1021/ic900059m

Direct Hydroxylation of Benzene to Phenol Using Hydrogen Peroxide Catalyzed by Nickel Complexes Supported by Pyridylalkylamine Ligands
journal, May 2015

  • Morimoto, Yuma; Bunno, Shuji; Fujieda, Nobutaka
  • Journal of the American Chemical Society, Vol. 137, Issue 18
  • DOI: 10.1021/jacs.5b01814

Electronic structure and reactivity of nickel( i ) pincer complexes: their aerobic transformation to peroxo species and site selective C–H oxygenation
journal, January 2016

  • Rettenmeier, Christoph A.; Wadepohl, Hubert; Gade, Lutz H.
  • Chemical Science, Vol. 7, Issue 6
  • DOI: 10.1039/c5sc04644k

Revisiting Alkane Hydroxylation with m ‐CPBA ( m ‐Chloroperbenzoic Acid) Catalyzed by Nickel(II) Complexes
journal, September 2021

  • Shinke, Tomoya; Itoh, Mayu; Wada, Takuma
  • Chemistry – A European Journal, Vol. 27, Issue 59
  • DOI: 10.1002/chem.202102532

Alkane and alkene oxidation reactions catalyzed by nickel(II) complexes: Effect of ligand factors
journal, January 2020

  • Sankaralingam, Muniyandi; Balamurugan, Mani; Palaniandavar, Mallayan
  • Coordination Chemistry Reviews, Vol. 403
  • DOI: 10.1016/j.ccr.2019.213085

Mechanistic studies of alkene epoxidation catalyzed by nickel(II) cyclam complexes. Oxygen-18 labeling and substituent effects
journal, August 1988

  • Kinneary, Joanne F.; Albert, Jeffrey S.; Burrows, Cynthia J.
  • Journal of the American Chemical Society, Vol. 110, Issue 18
  • DOI: 10.1021/ja00226a029

Can Ni Complexes Behave as Molecular Water Oxidation Catalysts?
journal, March 2019

Electrocatalytic Water Oxidation by a Water-Soluble Nickel Porphyrin Complex at Neutral pH with Low Overpotential
journal, May 2015

Catalytic Water Oxidation by a Bio-inspired Nickel Complex with a Redox-Active Ligand
journal, November 2017

Homogeneous Electrocatalytic Water Oxidation at Neutral pH by a Robust Macrocyclic Nickel(II) Complex
journal, September 2014

  • Zhang, Mei; Zhang, Ming-Tian; Hou, Cheng
  • Angewandte Chemie International Edition, Vol. 53, Issue 48
  • DOI: 10.1002/anie.201406983

Nickel: The “Spirited Horse” of Transition Metal Catalysis
journal, February 2015

Spectroscopic capture and reactivity of S = 1/2 nickel(iii)–oxygen intermediates in the reaction of a NiII-salt with mCPBA
journal, January 2012

  • Pfaff, Florian Felix; Heims, Florian; Kundu, Subrata
  • Chemical Communications, Vol. 48, Issue 31
  • DOI: 10.1039/c2cc30716b

Reactivity of a Nickel(II) Bis(amidate) Complex with meta -Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species
journal, August 2015

  • Corona, Teresa; Pfaff, Florian F.; Acuña-Parés, Ferran
  • Chemistry - A European Journal, Vol. 21, Issue 42
  • DOI: 10.1002/chem.201501841

Rapid Hydrogen and Oxygen Atom Transfer by a High-Valent Nickel–Oxygen Species
journal, September 2016

  • Corona, Teresa; Draksharapu, Apparao; Padamati, Sandeep K.
  • Journal of the American Chemical Society, Vol. 138, Issue 39
  • DOI: 10.1021/jacs.6b07544

Characterization and Reactivity of a Terminal Nickel(III)-Oxygen Adduct
journal, January 2015

  • Pirovano, Paolo; Farquhar, Erik R.; Swart, Marcel
  • Chemistry - A European Journal, Vol. 21, Issue 9
  • DOI: 10.1002/chem.201406485

Tuning the Reactivity of Terminal Nickel(III)–Oxygen Adducts for C–H Bond Activation
journal, October 2016

  • Pirovano, Paolo; Farquhar, Erik R.; Swart, Marcel
  • Journal of the American Chemical Society, Vol. 138, Issue 43
  • DOI: 10.1021/jacs.6b08406

Modulation of Nickel Pyridinedicarboxamidate Complexes to Explore the Properties of High-valent Oxidants
journal, January 2018

  • Pirovano, Paolo; Twamley, Brendan; McDonald, Aidan R.
  • Chemistry - A European Journal, Vol. 24, Issue 20
  • DOI: 10.1002/chem.201704618

Hydrogen Atom Transfer by a High-Valent Nickel-Chloride Complex
journal, January 2018

  • Mondal, Prasenjit; Pirovano, Paolo; Das, Ankita
  • Journal of the American Chemical Society, Vol. 140, Issue 5
  • DOI: 10.1021/jacs.7b11953

Stabilizing Terminal Ni(III)–Hydroxide Complex Using NNN-Pincer Ligands: Synthesis and Characterization
journal, April 2019

Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex
journal, January 2020

  • Fisher, Katherine J.; Feuer, Margalit L.; Lant, Hannah M. C.
  • Chemical Science, Vol. 11, Issue 6
  • DOI: 10.1039/c9sc05565g

Aromatic Methoxylation and Hydroxylation by Organometallic High-Valent Nickel Complexes
journal, June 2015

  • Zhou, Wen; Schultz, Jason W.; Rath, Nigam P.
  • Journal of the American Chemical Society, Vol. 137, Issue 24
  • DOI: 10.1021/jacs.5b04082

Oxidation of Ni(II) to Ni(IV) with Aryl Electrophiles Enables Ni-Mediated Aryl–CF 3 Coupling
journal, June 2015

  • Bour, James R.; Camasso, Nicole M.; Sanford, Melanie S.
  • Journal of the American Chemical Society, Vol. 137, Issue 25
  • DOI: 10.1021/jacs.5b04892

Accessing Pincer Bis(carbene) Ni(IV) Complexes from Ni(II) via Halogen and Halogen Surrogates
journal, March 2016

  • Martinez, Gabriel Espinosa; Ocampo, Cristian; Park, Yun Ji
  • Journal of the American Chemical Society, Vol. 138, Issue 13
  • DOI: 10.1021/jacs.5b12827

Oxidative C–C Bond Formation Reactivity of Organometallic Ni(II), Ni(III), and Ni(IV) Complexes
journal, December 2016

  • Watson, Michael B.; Rath, Nigam P.; Mirica, Liviu M.
  • Journal of the American Chemical Society, Vol. 139, Issue 1
  • DOI: 10.1021/jacs.6b10303

Oxidatively Induced C–H Activation at High Valent Nickel
journal, April 2017

  • Chong, Eugene; Kampf, Jeff W.; Ariafard, Alireza
  • Journal of the American Chemical Society, Vol. 139, Issue 17
  • DOI: 10.1021/jacs.7b02387

Aromatic Cyanoalkylation through Double C–H Activation Mediated by Ni(III)
journal, April 2016

  • Zhou, Wen; Zheng, Shuai; Schultz, Jason W.
  • Journal of the American Chemical Society, Vol. 138, Issue 18
  • DOI: 10.1021/jacs.6b02405

Synthesis, structure, spectroscopy and redox chemistry of square-planar nickel(ii) complexes with tetradentate o-phenylenedioxamidates and related ligands
journal, January 2005

  • Ottenwaelder, Xavier; Aukauloo, Ally; Journaux, Yves
  • Dalton Transactions, Issue 15
  • DOI: 10.1039/b502478a

A square-planar nickel(III) complex of an innocent ligand system
journal, June 1991

  • Collins, Terrence J.; Nichols, Thomas R.; Uffelman, Erich S.
  • Journal of the American Chemical Society, Vol. 113, Issue 12
  • DOI: 10.1021/ja00012a064

First Isolation and Structural Characterization of a Nickel(III) Complex Containing Aliphatic Thiolate Donors
journal, February 1998

Monovalent nickel in hydrogenase from Chromatium vinosum: Light sensitivity and evidence for direct interaction with hydrogen
journal, January 1985

Stable highly oxidizing cobalt complexes of macrocyclic ligands
journal, October 1991

  • Collins, Terrence J.; Powell, Richard D.; Slebodnick, Carla
  • Journal of the American Chemical Society, Vol. 113, Issue 22
  • DOI: 10.1021/ja00022a033

Stable Anilinyl Radicals Coordinated to Nickel: X‐ray Crystal Structure and Characterization
journal, November 2013

  • Kochem, Amélie; Gellon, Gisèle; Leconte, Nicolas
  • Chemistry – A European Journal, Vol. 19, Issue 49
  • DOI: 10.1002/chem.201303228

The Geometric and Electronic Structure of a One-Electron-Oxidized Nickel(II) Bis(salicylidene)diamine Complex
journal, July 2007

  • Storr, Tim; Wasinger, Erik C.; Pratt, Russell C.
  • Angewandte Chemie International Edition, Vol. 46, Issue 27
  • DOI: 10.1002/anie.200701194

Valence Tautomerism in Octahedral and Square-Planar Phenoxyl–Nickel(II) Complexes: Are Imino Nitrogen Atoms Good Friends?
journal, September 2006

  • Rotthaus, Olaf; Thomas, Fabrice; Jarjayes, Olivier
  • Chemistry - A European Journal, Vol. 12, Issue 26
  • DOI: 10.1002/chem.200600258

Stabilization of nickel(III) in a classical N2S2 coordination environment containing anionic sulfur
journal, November 1987

From metal to ligand electroactivity in nickel( ii ) oxamato complexes
journal, January 2004

  • Ottenwaelder, Xavier; Ruiz-García, Rafael; Blondin, Geneviève
  • Chem. Commun., Issue 5
  • DOI: 10.1039/b312295f

Reversible Double Oxidation and Protonation of the Non-Innocent Bridge in a Nickel(II) Salophen Complex
journal, November 2012

  • de Bellefeuille, David; Askari, Mohammad S.; Lassalle-Kaiser, Benedikt
  • Inorganic Chemistry, Vol. 51, Issue 23
  • DOI: 10.1021/ic301684h

Structure of the Ni Sites in Hydrogenases by X-ray Absorption Spectroscopy. Species Variation and the Effects of Redox Poise
journal, November 1996

  • Gu, Zhijie; Dong, Jun; Allan, Christian B.
  • Journal of the American Chemical Society, Vol. 118, Issue 45
  • DOI: 10.1021/ja962429p

Heterometallic Triiron-Oxo/Hydroxo Clusters: Effect of Redox-Inactive Metals
journal, December 2013

  • Herbert, David E.; Lionetti, Davide; Rittle, Jonathan
  • Journal of the American Chemical Society, Vol. 135, Issue 51
  • DOI: 10.1021/ja4104974

Redox-inactive metals modulate the reduction potential in heterometallic manganese–oxido clusters
journal, March 2013

  • Tsui, Emily Y.; Tran, Rosalie; Yano, Junko
  • Nature Chemistry, Vol. 5, Issue 4
  • DOI: 10.1038/nchem.1578

Trivalent Lewis Acidic Cations Govern the Electronic Properties and Stability of Heterobimetallic Complexes of Nickel
journal, November 2017

  • Kumar, Amit; Lionetti, Davide; Day, Victor W.
  • Chemistry - A European Journal, Vol. 24, Issue 1
  • DOI: 10.1002/chem.201704006

Redox Potential and Electronic Structure Effects of Proximal Nonredox Active Cations in Cobalt Schiff Base Complexes
journal, February 2017

Covalent radii revisited
journal, January 2008

  • Cordero, Beatriz; Gómez, Verónica; Platero-Prats, Ana E.
  • Dalton Transactions, Issue 21
  • DOI: 10.1039/b801115j

Molecular Double-Bond Covalent Radii for Elements Li–E112
journal, November 2009

  • Pyykkö, Pekka; Atsumi, Michiko
  • Chemistry - A European Journal, Vol. 15, Issue 46
  • DOI: 10.1002/chem.200901472

Highly Coordinated Heteronuclear Calcium–Iron Carbonyl Cation Complexes [CaFe(CO) n ] + ( n =5–12) with d−d Bonding
journal, May 2021

  • Jin, Xiaoyang; Bai, Yuna; Zhou, Yangyu
  • Angewandte Chemie International Edition, Vol. 60, Issue 25
  • DOI: 10.1002/anie.202103267

The Valence Orbitals of the Alkaline‐Earth Atoms
journal, September 2020

  • Fernández, Israel; Holzmann, Nicole; Frenking, Gernot
  • Chemistry – A European Journal, Vol. 26, Issue 62
  • DOI: 10.1002/chem.202002986

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

Proton-Coupled Electron Transfer in Biology: Results from Synergistic Studies in Natural and Model Systems
journal, June 2009

The Possible Role of Proton-Coupled Electron Transfer (PCET) in Water Oxidation by Photosystem II
journal, July 2007

  • Meyer, Thomas J.; Huynh, My Hang V.; Thorp, H. Holden
  • Angewandte Chemie International Edition, Vol. 46, Issue 28
  • DOI: 10.1002/anie.200600917

The roles of long-range proton-coupled electron transfer in the directionality and efficiency of [FeFe]-hydrogenases
journal, August 2020

  • Lampret, Oliver; Duan, Jifu; Hofmann, Eckhard
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 34
  • DOI: 10.1073/pnas.2007090117

Manifesto on the Thermochemistry of Nanoscale Redox Reactions for Energy Conversion
journal, March 2019

Proton-Coupled Electron Transfer Reactions Catalysed by 3 d Metal Complexes
journal, August 2015

Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins
journal, October 2014

  • Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 42
  • DOI: 10.1073/pnas.1414908111

A Nickel Dithiolate Water Reduction Catalyst Providing Ligand-Based Proton-Coupled Electron-Transfer Pathways
journal, March 2017

  • Koshiba, Keita; Yamauchi, Kosei; Sakai, Ken
  • Angewandte Chemie International Edition, Vol. 56, Issue 15
  • DOI: 10.1002/anie.201700927

The Mechanism of Homogeneous CO 2 Reduction by Ni(cyclam): Product Selectivity, Concerted Proton–Electron Transfer and C–O Bond Cleavage
journal, June 2014

  • Song, Jinshuai; Klein, Eric L.; Neese, Frank
  • Inorganic Chemistry, Vol. 53, Issue 14
  • DOI: 10.1021/ic500829p

Remote Nickel-Catalyzed Cross-Coupling Arylation via Proton-Coupled Electron Transfer-Enabled C–C Bond Cleavage
journal, February 2020

  • Huang, Long; Ji, Tengfei; Rueping, Magnus
  • Journal of the American Chemical Society, Vol. 142, Issue 7
  • DOI: 10.1021/jacs.9b12490

Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications
journal, December 2010

  • Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M.
  • Chemical Reviews, Vol. 110, Issue 12
  • DOI: 10.1021/cr100085k

A Continuum of Proton-Coupled Electron Transfer Reactivity
journal, September 2018

  • Darcy, Julia W.; Koronkiewicz, Brian; Parada, Giovanny A.
  • Accounts of Chemical Research, Vol. 51, Issue 10
  • DOI: 10.1021/acs.accounts.8b00319

Proton-Coupled Electron Transfer Guidelines, Fair and Square
journal, January 2021

  • Tyburski, Robin; Liu, Tianfei; Glover, Starla D.
  • Journal of the American Chemical Society, Vol. 143, Issue 2
  • DOI: 10.1021/jacs.0c09106

The Essential Role of Bond Energetics in C–H Activation/Functionalization
journal, March 2017

Proton-Coupled Electron Transfer of Ruthenium(III)−Pterin Complexes: A Mechanistic Insight
journal, August 2009

  • Miyazaki, Soushi; Kojima, Takahiko; Mayer, James M.
  • Journal of the American Chemical Society, Vol. 131, Issue 32
  • DOI: 10.1021/ja904386r

Thermodynamics of a μ-oxo Dicopper(II) Complex for Hydrogen Atom Abstraction
journal, December 2017

  • Ali, Ghazanfar; VanNatta, Peter E.; Ramirez, David A.
  • Journal of the American Chemical Society, Vol. 139, Issue 51
  • DOI: 10.1021/jacs.7b10833

Understanding Hydrogen Atom Transfer: From Bond Strengths to Marcus Theory
journal, January 2011

  • Mayer, James M.
  • Accounts of Chemical Research, Vol. 44, Issue 1
  • DOI: 10.1021/ar100093z

Elektronentransferreaktionen in der Chemie - Theorie und Experiment (Nobel-Vortrag)
journal, August 1993

Electron Transfer Reactions in Chemistry: Theory and Experiment (Nobel Lecture)
journal, August 1993

  • Marcus, Rudolph A.
  • Angewandte Chemie International Edition in English, Vol. 32, Issue 8
  • DOI: 10.1002/anie.199311113

Electron-transfer properties of high-valent metal-oxo complexes
journal, May 2013

Large Ground-State Entropy Changes for Hydrogen Atom Transfer Reactions of Iron Complexes
journal, April 2007

  • Mader, Elizabeth A.; Davidson, Ernest R.; Mayer, James M.
  • Journal of the American Chemical Society, Vol. 129, Issue 16
  • DOI: 10.1021/ja0686918

Switchover of the Mechanism between Electron Transfer and Hydrogen-Atom Transfer for a Protonated Manganese(IV)-Oxo Complex by Changing Only the Reaction Temperature
journal, May 2016

  • Jung, Jieun; Kim, Surin; Lee, Yong-Min
  • Angewandte Chemie International Edition, Vol. 55, Issue 26
  • DOI: 10.1002/anie.201602460

Second‐Coordination Sphere Effects on Selectivity and Specificity of Heme and Nonheme Iron Enzymes
journal, February 2020

Proton-Coupled Electron Transfer in Duplex DNA:  Driving Force Dependence and Isotope Effects on Electrocatalytic Oxidation of Guanine
journal, January 2001

  • Weatherly, Stephanie C.; Yang, Ivana V.; Thorp, H. Holden
  • Journal of the American Chemical Society, Vol. 123, Issue 6
  • DOI: 10.1021/ja003788u

Linear free energy relations for multielectron transfer kinetics: a brief look at the Broensted/Tafel analogy
journal, March 1990

  • Ram, M. S.; Hupp, Joseph T.
  • The Journal of Physical Chemistry, Vol. 94, Issue 6
  • DOI: 10.1021/j100369a035

Oxidation Mechanism of Phenols by Dicopper−Dioxygen (Cu2/O2) Complexes
journal, August 2003

  • Osako, Takao; Ohkubo, Kei; Taki, Masayasu
  • Journal of the American Chemical Society, Vol. 125, Issue 36
  • DOI: 10.1021/ja029380+

Mechanistic Insights into the Oxidation of Substituted Phenols via Hydrogen Atom Abstraction by a Cupric–Superoxo Complex
journal, July 2014

  • Lee, Jung Yoon; Peterson, Ryan L.; Ohkubo, Kei
  • Journal of the American Chemical Society, Vol. 136, Issue 28
  • DOI: 10.1021/ja503105b

Hydrogen Atom Abstraction by High-Valent Fe(OH) versus Mn(OH) Porphyrinoid Complexes: Mechanistic Insights from Experimental and Computational Studies
journal, November 2019

Phenol Oxidation by a Nickel(III)–Fluoride Complex: Exploring the Influence of the Proton Accepting Ligand in PCET Oxidation
journal, July 2020

  • Mondal, Prasenjit; McDonald, Aidan R.
  • Chemistry – A European Journal, Vol. 26, Issue 44
  • DOI: 10.1002/chem.202002135

Electrophilic Arene Hydroxylation and Phenol OH Oxidations Performed by an Unsymmetric μ-η1:η1-O2-Peroxo Dicopper(II) Complex
journal, January 2012

  • Garcia-Bosch, Isaac; Ribas, Xavi; Costas, Miquel
  • Chemistry - A European Journal, Vol. 18, Issue 7
  • DOI: 10.1002/chem.201102372

Mechanism of phenol oxidation by heterodinuclear Ni Cu bis(μ-oxo) complexes involving nucleophilic oxo groups
journal, January 2014

  • Kundu, Subrata; Miceli, Enrico; Farquhar, Erik R.
  • Dalton Trans., Vol. 43, Issue 11
  • DOI: 10.1039/c3dt52644e

Reactivity of the copper( iii )-hydroxide unit with phenols
journal, January 2017

  • Dhar, Debanjan; Yee, Gereon M.; Markle, Todd F.
  • Chemical Science, Vol. 8, Issue 2
  • DOI: 10.1039/c6sc03039d

Structure, Spectroscopy, and Reactivity of a Mononuclear Copper Hydroxide Complex in Three Molecular Oxidation States
journal, June 2020

  • Wu, Tong; MacMillan, Samantha N.; Rajabimoghadam, Khashayar
  • Journal of the American Chemical Society, Vol. 142, Issue 28
  • DOI: 10.1021/jacs.0c03867

A High‐Valent Manganese(IV)–Oxo–Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity
journal, November 2019

  • Karmalkar, Deepika G.; Sankaralingam, Muniyandi; Seo, Mi Sook
  • Angewandte Chemie International Edition, Vol. 58, Issue 45
  • DOI: 10.1002/anie.201910032

Significantly shorter Fe–S bond in cytochrome P450-I is consistent with greater reactivity relative to chloroperoxidase
journal, August 2015

  • Krest, Courtney M.; Silakov, Alexey; Rittle, Jonathan
  • Nature Chemistry, Vol. 7, Issue 9
  • DOI: 10.1038/nchem.2306

Characterization of a selenocysteine-ligated P450 compound I reveals direct link between electron donation and reactivity
journal, May 2017

  • Onderko, Elizabeth L.; Silakov, Alexey; Yosca, Timothy H.
  • Nature Chemistry, Vol. 9, Issue 7
  • DOI: 10.1038/nchem.2781
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