Synthetically Reversible, Proton-Mediated Nitrite N–O Bond Cleavage at a Dicopper Site

Fernandez, Jose Martinez; Javadi, Alireza Haji Seyed; Teat, Simon J.; Cundari, Thomas R.; Tilley, T. Don

doi:10.1021/jacs.4c14642

Synthetically Reversible, Proton-Mediated Nitrite N–O Bond Cleavage at a Dicopper Site

Journal Article · Tue Dec 10 00:00:00 EST 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c14642· OSTI ID:2480763

^[1]; Javadi, Alireza Haji Seyed ^[2]; Teat, Simon J. ^[3]; ^[2]; ^[1]

University of California, Berkeley, CA (United States)
University of North Texas, Denton, TX (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

A monocationic dicopper(I,I) nitrite complex [Cu₂(μ-κ¹:κ¹-O₂N)DPFN][NTf₂] (2) (DPFN = 2,7-bis(fluoro-di(2-pyridyl)methyl)-1,8-naphthyridine, NTf₂^– = N(SO₂CF₃)₂^–), was synthesized by treatment of a dicopper acetonitrile complex, [Cu₂(μ-MeCN)DPFN][NTf₂]₂ (1), with tetrabutylammonium nitrite ([nBu₄N][NO₂]). DFT calculations indicate that 2 is one of three linkage isomers that are close in energy and presumably accessible in solution. Reaction of the μ-κ¹:κ¹-O₂N complex with p-TolSH produces nitrous acid (HONO) and the corresponding dicopper thiolate species via an acid–base exchange reaction. Notably, treatment of 2 with HNTf₂ results in N–O bond cleavage in the putative, HONO-ligated complex to form the more thermodynamically favorable nitrosyl-bridged dicopper complex [Cu₂(μ-NO)(μ-OH)DPFN][NTf₂]₂ (4). This scission can be reversed via deprotonation of the hydroxy ligand with KO^tBu. X-ray diffraction studies confirmed the solid-state molecular structures of 2 and 4. DFT calculations were used to construct a reaction coordinate diagram detailing formation of the μ-NO complex and to describe its electronic structure. The nitrosyl ligand in 4 is chemically labile, as demonstrated by its ready displacement in reactions with CO or NO₂^–.

View Journal Article

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)

Sponsoring Organization:: National Institutes of Health (NIH); National Science Foundation (NSF); US Department of Energy; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; FG02-03ER15387

OSTI ID:: 2480763

Alternate ID(s):: OSTI ID: 2482246
OSTI ID: 2568342

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 50 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (58)

Spectroscopic Characterization of Reaction Intermediates in a Model for Copper Nitrite Reductase Kujime, Masato; Fujii, Hiroshi Angewandte Chemie International Edition, Vol. 45, Issue 7 https://doi.org/10.1002/anie.200503555	journal	January 2006
A Dicopper Platform that Stabilizes the Formation of Pentanuclear Coinage Metal Hydride Complexes Desnoyer, Addison N.; Nicolay, Amélie; Ziegler, Micah S. Angewandte Chemie International Edition, Vol. 59, Issue 31 https://doi.org/10.1002/anie.202004346	journal	May 2020
Redox‐Neutral S ‐nitrosation Mediated by a Dicopper Center Tao, Wenjie; Moore, Curtis E.; Zhang, Shiyu Angewandte Chemie International Edition, Vol. 60, Issue 29 https://doi.org/10.1002/anie.202102589	journal	June 2021
An effortless approach to synthesize two structurally diverse nano copper(II) materials and assessment of their apoptosis‐inducing ability on lung cancer cell line Biswas, Sneha; Karim, Suhana; Zangrando, Ennio Applied Organometallic Chemistry, Vol. 36, Issue 5 https://doi.org/10.1002/aoc.6659	journal	March 2022
Cu ^I and Cu ^II Complexes Containing Nitrite and Tridentate Aromatic Amine Ligand as Models for the Substrate‐Binding Type‐2 Cu Site of Nitrite Reductase Yokoyama, Hiroshi; Yamaguchi, Kazuya; Sugimoto, Manabu European Journal of Inorganic Chemistry, Vol. 2005, Issue 8 https://doi.org/10.1002/ejic.200400808	journal	April 2005
Copper(II)nitrito complexes with 2,2′-dipyridylamine. Crystal structures of the [(acetato)(2,2′-dipyridylamine)(nitrito-O,O′)copper(II)] and [(2,2′-dipyridylamine) (nitrito-O,O′)(μ-nitrito-O)copper(II)]2·2(acetonitrile) Camus, Annamaria; Marsich, Nazario; Manotti Lanfredi, Anna Maria Inorganica Chimica Acta, Vol. 309, Issue 1-2 https://doi.org/10.1016/S0020-1693(00)00213-9	journal	November 2000
Copper(II) nitrite complexes of tripodal ligands derived from 1,1,1-tris(2-pyridyl)methylamine Arnold, Phillip J.; Davies, Sian C.; Durrant, Marcus C. Inorganica Chimica Acta, Vol. 348 https://doi.org/10.1016/S0020-1693(02)01487-1	journal	May 2003
Synthesis, characterization and protonation reaction of copper and palladium complexes bearing nitrite ligands in O,O-bidentate and N-monodentate bonding fashions Chen, Chi-Shian; Dai, Huei-Fang; Chen, Chia-Hsiang Inorganica Chimica Acta, Vol. 376, Issue 1 https://doi.org/10.1016/j.ica.2011.06.052	journal	October 2011
On the chemical biology of the nitrite/sulfide interaction Cortese-Krott, Miriam M.; Fernandez, Bernadette O.; Kelm, Malte Nitric Oxide, Vol. 46 https://doi.org/10.1016/j.niox.2014.12.009	journal	April 2015
Coordination polymers and molecular structures among complexes of mercury(II) halides with selected 1-benzoylthioureas Okuniewski, Andrzej; Rosiak, Damian; Chojnacki, Jarosław Polyhedron, Vol. 90 https://doi.org/10.1016/j.poly.2015.01.035	journal	April 2015
Bimetallics in a Nutshell: Complexes Supported by Chelating Naphthyridine-Based Ligands Desnoyer, Addison N.; Nicolay, Amélie; Rios, Pablo Accounts of Chemical Research, Vol. 53, Issue 9 https://doi.org/10.1021/acs.accounts.0c00382	journal	September 2020
Mechanism of O-Atom Transfer from Nitrite: Nitric Oxide Release at Copper(II) Stauffer, Molly; Sakhaei, Zeinab; Greene, Christine Inorganic Chemistry, Vol. 60, Issue 21 https://doi.org/10.1021/acs.inorgchem.1c00625	journal	June 2021
Involvement of a Formally Copper(III) Nitrite Complex in Proton-Coupled Electron Transfer and Nitration of Phenols Bouchey, Caitlin J.; Tolman, William B. Inorganic Chemistry, Vol. 61, Issue 5 https://doi.org/10.1021/acs.inorgchem.1c03790	journal	January 2022
Exploring Photoswitchable Properties of Two Nitro Nickel(II) Complexes with (N,N,O)-Donor Ligands and Their Copper(II) Analogues Borowski, Patryk; Kutniewska, Sylwia E.; Kamiński, Radosław Inorganic Chemistry, Vol. 61, Issue 17 https://doi.org/10.1021/acs.inorgchem.2c00526	journal	April 2022
Dicopper Alkyl Complexes: Synthesis, Structure, and Unexpected Persistence Ziegler, Micah S.; Torquato, Nicole A.; Levine, Daniel S. Organometallics, Vol. 37, Issue 16 https://doi.org/10.1021/acs.organomet.8b00443	journal	August 2018
Proton-Coupled Electron Transfer Enhances the Electrocatalytic Reduction of Nitrite to NO in a Bioinspired Copper Complex Cioncoloni, Giacomo; Roger, Isolda; Wheatley, Paul S. ACS Catalysis, Vol. 8, Issue 6 https://doi.org/10.1021/acscatal.8b00361	journal	April 2018
Electrochemically Modulated Nitric Oxide (NO) Releasing Biomedical Devices via Copper(II)-Tri(2-pyridylmethyl)amine Mediated Reduction of Nitrite Ren, Hang; Wu, Jianfeng; Xi, Chuanwu ACS Applied Materials & Interfaces, Vol. 6, Issue 6 https://doi.org/10.1021/am406066a	journal	March 2014
Catalytic Function and Local Proton Structure at the Type 2 Copper of Nitrite Reductase: The Correlation of Enzymatic pH Dependence, Conserved Residues, and Proton Hyperfine Structure Zhao, Yiwei; Lukoyanov, Dmitriy A.; Toropov, Yuriy V. Biochemistry, Vol. 41, Issue 23 https://doi.org/10.1021/bi0256274	journal	May 2002
Bidirectional Catalysis by Copper-Containing Nitrite Reductase ^† Wijma, Hein J.; Canters, Gerard W.; de Vries, Simon Biochemistry, Vol. 43, Issue 32 https://doi.org/10.1021/bi0496687	journal	August 2004
How Biology Handles Nitrite Maia, Luisa B.; Moura, José J. G. Chemical Reviews, Vol. 114, Issue 10 https://doi.org/10.1021/cr400518y	journal	April 2014
Synthesis and Spectroscopic Characterization of Copper(II)−Nitrito Complexes with Hydrotris(pyrazolyl)borate and Related Coligands Lehnert, Nicolai; Cornelissen, Ursula; Neese, Frank Inorganic Chemistry, Vol. 46, Issue 10 https://doi.org/10.1021/ic0619355	journal	May 2007
Characterization of A New Copper(I)−Nitrito Complex That Evolves Nitric Oxide Chuang, Wan-Jung; Lin, I-Jung; Chen, Hsing-Yin Inorganic Chemistry, Vol. 49, Issue 12 https://doi.org/10.1021/ic100083b	journal	May 2010
Hydrotris(triazolyl)borate Complexes as Functional Models for Cu Nitrite Reductase: The Electronic Influence of Distal Nitrogens Kumar, Mukesh; Dixon, Natalie A.; Merkle, Anna C. Inorganic Chemistry, Vol. 51, Issue 13 https://doi.org/10.1021/ic300160c	journal	June 2012
Copper(I) Nitro Complex with an Anionic [HB(3,5-Me₂Pz)₃]⁻ Ligand: A Synthetic Model for the Copper Nitrite Reductase Active Site Hsu, Sodio C. N.; Chang, Yu-Lun; Chuang, Wan-Jung Inorganic Chemistry, Vol. 51, Issue 17 https://doi.org/10.1021/ic300932a	journal	August 2012
Copper Complexes Relevant to the Catalytic Cycle of Copper Nitrite Reductase: Electrochemical Detection of NO(g) Evolution and Flipping of NO₂ Binding Mode upon Cu^II → Cu^I Reduction Maji, Ram Chandra; Barman, Suman Kumar; Roy, Suprakash Inorganic Chemistry, Vol. 52, Issue 19 https://doi.org/10.1021/ic401295t	journal	September 2013
Synthetic Analogs of Nitrite Adducts of Copper Proteins: Characterization and Interconversion of Dicopper(I,I) and -(I,II) Complexes Bridged Only by NO2- Halfen, Jason A.; Mahapatra, Samiran; Olmstead, Marilyn M. Journal of the American Chemical Society, Vol. 116, Issue 5 https://doi.org/10.1021/ja00084a079	journal	March 1994
Isolation and x-ray structure of a dinuclear copper-nitrosyl complex Paul, Partha P.; Tyeklar, Zoltan; Farooq, Amjad Journal of the American Chemical Society, Vol. 112, Issue 6 https://doi.org/10.1021/ja00162a060	journal	March 1990
Effect of a Tridentate Ligand on the Structure, Electronic Structure, and Reactivity of the Copper(I) Nitrite Complex: Role of the Conserved Three-Histidine Ligand Environment of the Type-2 Copper Site in Copper-Containing Nitrite Reductases Kujime, Masato; Izumi, Chiemi; Tomura, Masaaki Journal of the American Chemical Society, Vol. 130, Issue 19 https://doi.org/10.1021/ja075575b	journal	April 2008
Selective Nitrite Reduction at Heterobimetallic CoMg Complexes Uyeda, Christopher; Peters, Jonas C. Journal of the American Chemical Society, Vol. 135, Issue 32 https://doi.org/10.1021/ja4053653	journal	July 2013
NO ₂ ^– Activation and Reduction to NO by a Nonheme Fe(NO ₂ ) ₂ Complex Sanders, Brian C.; Hassan, Sayed M.; Harrop, Todd C. Journal of the American Chemical Society, Vol. 136, Issue 29 https://doi.org/10.1021/ja505236x	journal	July 2014
Spectroscopic and Computational Studies of Nitrite Reductase: Proton Induced Electron Transfer and Backbonding Contributions to Reactivity Ghosh, Somdatta; Dey, Abhishek; Sun, Yan Journal of the American Chemical Society, Vol. 131, Issue 1 https://doi.org/10.1021/ja806873e	journal	December 2008
Synthetic Modeling of Nitrite Binding and Activation by Reduced Copper Proteins. Characterization of Copper(I)−Nitrite Complexes That Evolve Nitric Oxide Halfen, Jason A.; Mahapatra, Samiran; Wilkinson, Elizabeth C. Journal of the American Chemical Society, Vol. 118, Issue 4 https://doi.org/10.1021/ja952691i	journal	January 1996
A Dicopper Nitrenoid by Oxidation of a Cu ^I Cu ^I Core: Synthesis, Electronic Structure, and Reactivity Desnoyer, Addison N.; Nicolay, Amélie; Ziegler, Micah S. Journal of the American Chemical Society, Vol. 143, Issue 18 https://doi.org/10.1021/jacs.1c02235	journal	April 2021
Controlling the Direction of S-Nitrosation versus Denitrosation: Reversible Cleavage and Formation of an S–N Bond within a Dicopper Center Tao, Wenjie; Yerbulekova, Alina; Moore, Curtis E. Journal of the American Chemical Society, Vol. 144, Issue 7 https://doi.org/10.1021/jacs.1c12799	journal	February 2022
Aryl Group Transfer from Tetraarylborato Anions to an Electrophilic Dicopper(I) Center and Mixed-Valence μ-Aryl Dicopper(I,II) Complexes Ziegler, Micah S.; Levine, Daniel S.; Lakshmi, K. V. Journal of the American Chemical Society, Vol. 138, Issue 20 https://doi.org/10.1021/jacs.6b00802	journal	May 2016
Copper(II) Activation of Nitrite: Nitrosation of Nucleophiles and Generation of NO by Thiols Kundu, Subrata; Kim, William Y.; Bertke, Jeffery A. Journal of the American Chemical Society, Vol. 139, Issue 3 https://doi.org/10.1021/jacs.6b11332	journal	December 2016
Dicopper μ-Oxo, μ-Nitrosyl Complex from the Activation of NO or Nitrite at a Dicopper Center Tao, Wenjie; Bower, Jamey K.; Moore, Curtis E. Journal of the American Chemical Society, Vol. 141, Issue 26 https://doi.org/10.1021/jacs.9b03635	journal	May 2019
Phenol Reduces Nitrite to NO at Copper(II): Role of a Proton-Responsive Outer Coordination Sphere in Phenol Oxidation Mondal, Aditesh; Reddy, Kiran P.; Bertke, Jeffery A. Journal of the American Chemical Society, Vol. 142, Issue 4 https://doi.org/10.1021/jacs.9b11597	journal	January 2020
Structural variation in copper( i ) complexes with pyridylmethylamide ligands: structural analysis with a new four-coordinate geometry index, τ ₄ Yang, Lei; Powell, Douglas R.; Houser, Robert P. Dalton Trans., Issue 9 https://doi.org/10.1039/B617136B	journal	January 2007
Nitritereduction by copper complexes Woollard-Shore, John G.; Holland, Jason P.; Jones, Michael W. Dalton Trans., Vol. 39, Issue 6 https://doi.org/10.1039/B913463H	journal	January 2010
First example of a Cu( i )–(η ² -O,O)nitrite complex derived from Cu( ii )–nitrosyl Kalita, Apurba; Kumar, Pankaj; Deka, Ramesh C. Chem. Commun., Vol. 48, Issue 9 https://doi.org/10.1039/C1CC16316G	journal	January 2012
Conversion of nitrite to nitric oxide at zinc via S-nitrosothiols Cardenas, Allan Jay P.; Abelman, Rebecca; Warren, Timothy H. Chem. Commun., Vol. 50, Issue 2 https://doi.org/10.1039/C3CC46102E	journal	January 2014
Nitrite reduction by copper through ligand-mediated proton and electron transfer Moore, Cameron M.; Szymczak, Nathaniel K. Chemical Science, Vol. 6, Issue 6 https://doi.org/10.1039/C5SC00720H	journal	January 2015
Structure and nitrite reduction reactivity study of bio-inspired copper(i)–nitro complexes in steric and electronic considerations of tridentate nitrogen ligands Chang, Yu-Lun; Lin, Ya-Fan; Chuang, Wan-Jung Dalton Transactions, Vol. 47, Issue 15 https://doi.org/10.1039/C7DT03843G	journal	January 2018
Nitric oxide-release study of a bio-inspired copper(i)-nitrito complex under chemical and biological conditions Chuang, Wan-Jung; Narwane, Manmath; Chen, Hsing-Yin Dalton Transactions, Vol. 47, Issue 37 https://doi.org/10.1039/C8DT02281J	journal	January 2018
Nitric oxide generation study of unsymmetrical β-diketiminato copper(ii) nitrite complexes Chand, Kuldeep; Chu, Yu-Cheng; Wang, Tzai-Wei Dalton Transactions, Vol. 51, Issue 9 https://doi.org/10.1039/D1DT03711K	journal	January 2022
Synthesis, structure, and spectroscopic properties of copper( II ) compounds containing nitrogen–sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper( II ) perchlorate Addison, Anthony W.; Rao, T. Nageswara; Reedijk, Jan J. Chem. Soc., Dalton Trans., Issue 7 https://doi.org/10.1039/DT9840001349	journal	January 1984
Unique cationic, neutral and anionic copper(ii) nitrite species in a single compound Blake, Alexander J.; Hill, Stuart J.; Hubberstey, Peter Chemical Communications, Issue 15 https://doi.org/10.1039/a803762k	journal	January 1998
Polynuclear and 1-D derivatives of 1,3-bis(dimethylamino)-2-propanolato ligand. Structure and magnetic characterization Escuer, Albert; El Fallah, M. Salah; Vicente, Ramon Dalton Transactions, Issue 12 https://doi.org/10.1039/b402629b	journal	January 2004
Coordination of NO2− ligand to Cu(i) ion in an O,O-bidentate fashion that evolves NO gas upon protonation: a model reaction relevant to the denitrification process Chen, Chi-Shian; Yeh, Wen-Yann Chemical Communications, Vol. 46, Issue 18 https://doi.org/10.1039/b927513d	journal	January 2010
Atomic resolution structures of resting-state, substrate- and product-complexed Cu-nitrite reductase provide insight into catalytic mechanism Antonyuk, S. V.; Strange, R. W.; Sawers, G. Proceedings of the National Academy of Sciences, Vol. 102, Issue 34 https://doi.org/10.1073/pnas.0504207102	journal	August 2005
The Structure of Copper-nitrite Reductase from Achromobacter cycloclastes at Five pH Values, with NO-2 Bound and with Type II Copper Depleted Adman, Elinor T.; Godden, J. W.; Turley, Stewart Journal of Biological Chemistry, Vol. 270, Issue 46 https://doi.org/10.1074/jbc.270.46.27458	journal	November 1995
Characterization of a Nitrite Reductase Involved in Nitrifier Denitrification Lawton, Thomas J.; Bowen, Kimberly E.; Sayavedra-Soto, Luis A. Journal of Biological Chemistry, Vol. 288, Issue 35 https://doi.org/10.1074/jbc.M113.484543	journal	August 2013
An investigation into the unusual linkage isomerization and nitrite reduction activity of a novel tris(2-pyridyl) copper complex Roger, Isolda; Wilson, Claire; Senn, Hans M. Royal Society Open Science, Vol. 4, Issue 8 https://doi.org/10.1098/rsos.170593	journal	August 2017
(Nitrito-O,O')bis(triphenylphosphine)copper(I), (PPh3)2Cu(NO2-O,O') Halfen, J. A.; Tolman, W. B. Acta Crystallographica Section C Crystal Structure Communications, Vol. 51, Issue 2 https://doi.org/10.1107/S0108270194008991	journal	February 1995
Side-On Copper-Nitrosyl Coordination by Nitrite Reductase Tocheva, E. I. Science, Vol. 304, Issue 5672 https://doi.org/10.1126/science.1095109	journal	May 2004
The 2.3 angstrom X-ray structure of nitrite reductase from Achromobacter cycloclastes Godden, J.; Turley, S.; Teller, D. Science, Vol. 253, Issue 5018 https://doi.org/10.1126/science.1862344	journal	July 1991
Anion Capture at the Open Core of a Geometrically Flexible Dicopper(II,II) Macrocycle Complex Brooks, Sam H.; Richards, Corey A.; Carroll, Patrick J. Inorganics, Vol. 11, Issue 9 https://doi.org/10.3390/inorganics11090348	journal	August 2023

Similar Records

A Dicopper Nitrenoid by Oxidation of a Cu'Cu' Core: Synthesis, Electronic Structure, and Reactivity

Journal Article · Mon Apr 19 20:00:00 EDT 2021 · Journal of the American Chemical Society · OSTI ID:1831110

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Anions
Binding modes
Ligands
Molecular structure
Nitrosyls

Synthetically Reversible, Proton-Mediated Nitrite N–O Bond Cleavage at a Dicopper Site

Citation Formats

References (58)

Similar Records

Related Subjects