Metal–Ligand Proton Tautomerism, Electron Transfer, and C(sp 3 )–H Activation by a 4-Pyridinyl-Pincer Iridium Hydride Complex

Bhatti, Tariq M.; Kumar, Akshai; Parihar, Ashish; Moncy, Hellan K.; Emge, Thomas J.; Waldie, Kate M.; Hasanayn, Faraj; Goldman, Alan S.

doi:10.1021/jacs.3c03376

Metal–Ligand Proton Tautomerism, Electron Transfer, and C(sp ³ )–H Activation by a 4-Pyridinyl-Pincer Iridium Hydride Complex

Journal Article · Tue Aug 08 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c03376· OSTI ID:1994228

Bhatti, Tariq M. ^[1]; ^[2]; Parihar, Ashish ^[1]; Moncy, Hellan K. ^[1]; Emge, Thomas J. ^[1]; ^[1]; ^[3]; ^[4]

Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, United States
Centre for Nanotechnology, Indian Institute of Technology Guwahati, Guwahati 781039, Assam, India
Department of Chemistry, American University of Beirut, Beirut 1107 2020, Lebanon
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, United States, Centre for Nanotechnology, Indian Institute of Technology Guwahati, Guwahati 781039, Assam, India

Not Available

View Journal Article

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0020139

OSTI ID:: 1994228

Alternate ID(s):: OSTI ID: 2001035
OSTI ID: 1996372

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 33 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (69)

Highly Active and Recyclable Heterogeneous Iridium Pincer Catalysts for Transfer Dehydrogenation of Alkanes Huang, Zheng; Brookhart, Maurice; Goldman, Alan S. Advanced Synthesis & Catalysis, Vol. 351, Issue 1-2 https://doi.org/10.1002/adsc.200800615	journal	January 2009
Katalytische Umsetzungen von Olefinen an Platinmetall-Verbindungen Das Consortium-Verfahren zur Herstellung von Acetaldehyd Smidt, J.; Hafner, W.; Jira, R. Angewandte Chemie, Vol. 71, Issue 5 https://doi.org/10.1002/ange.19590710503	journal	March 1959
Metallacyclic Pyridylidene Structures from Reactions of Terminal Pyridylidenes with Alkenes and Acetylene Álvarez, Eleuterio; Hernández, Yohar A.; López-Serrano, Joaquín Angewandte Chemie International Edition, Vol. 49, Issue 20 https://doi.org/10.1002/anie.201000608	journal	April 2010
The Nickel-Pincer Complex in Lactate Racemase Is an Electron Relay and Sink that acts through Proton-Coupled Electron Transfer Wang, Binju; Shaik, Sason Angewandte Chemie International Edition, Vol. 56, Issue 34 https://doi.org/10.1002/anie.201612065	journal	February 2017
Functional Models of the Nickel Pincer Nucleotide Cofactor of Lactate Racemase Shi, Renyi; Wodrich, Matthew D.; Pan, Hui‐Jie Angewandte Chemie International Edition, Vol. 58, Issue 47 https://doi.org/10.1002/anie.201910490	journal	November 2019
A Novel Nickel Pincer Complex in the Active Site of Lactate Racemase Xu, Tao; Bauer, Gerald; Hu, Xile ChemBioChem, Vol. 17, Issue 1 https://doi.org/10.1002/cbic.201500498	journal	November 2015
Alternative Mechanistic Strategy for Enzyme Catalysis in a Ni-Dependent Lactate Racemase (LarA): Intermediate Destabilization by the Cofactor Zhang, Xiaoyong; Chung, Lung W. Chemistry - A European Journal, Vol. 23, Issue 15 https://doi.org/10.1002/chem.201604893	journal	December 2016
Preparation of Remote NHC Complexes of Rhodium(I) and Gold(I) by Ligand Transfer Strasser, Christoph E.; Stander‐Grobler, Elzet; Schuster, Oliver European Journal of Inorganic Chemistry, Vol. 2009, Issue 13 https://doi.org/10.1002/ejic.200801180	journal	April 2009
The Nature of the Metal–Carbene Bond in Normal and Abnormal Pyridylidene, Quinolylidene and Isoquinolylidene Complexes Heydenrych, Greta; von Hopffgarten, Moritz; Stander, Elzet European Journal of Inorganic Chemistry, Vol. 2009, Issue 13 https://doi.org/10.1002/ejic.200801244	journal	April 2009
Reactions of iridium bis(phosphinite) pincer complexes with protic acids Polukeev, A. V.; Kuklin, S. A.; Petrovskii, P. V. Russian Chemical Bulletin, Vol. 59, Issue 4 https://doi.org/10.1007/s11172-010-0156-6	journal	April 2010
N-protonated 2-pyridylnickel(II) complexes insertion of isocyanides into the nickel2-pyridyl bond Crociani, Bruno; Di Bianca, Francesca; Giovenco, Amalia Journal of Organometallic Chemistry, Vol. 323, Issue 1 https://doi.org/10.1016/0022-328X(87)87134-6	journal	April 1987
Organometallic nucleophiles. Mechanism of halide displacement at saturated carbon by 2-pyridyl and 4-Pyridyl complexes [M(dmtc)(C5H4N-Cn)(L)] (M  Pd, Pt; dmtc  dimethyldithiocarbamate; n  2,4; L  Canovese, L.; Uguagliati, P.; Di Bianca, F. Journal of Organometallic Chemistry, Vol. 438, Issue 1-2 https://doi.org/10.1016/0022-328X(92)88023-C	journal	October 1992
A powerful organometallic nucleophile the 2-pyridyl group in (dimethyldithio-carbamate) (2-pyridyl)(triphenyl-phosphine)platinum(II) Crociani, Bruno; Di Bianca, Francesca; Uguagliati, Paolo Inorganica Chimica Acta, Vol. 176, Issue 1 https://doi.org/10.1016/S0020-1693(00)85080-X	journal	October 1990
Insertion of isocyanides into the palladium—carbon bond of C2-palladated heterocycles. Synthesis of trans-[PdCl{C(RN)NR}(PPh3)2] complexes (RN = 2-pyridyl, 2-pyrazyl; R = alkyl or aryl group) Crociani, Bruno; Dibianca, Francesca; Bertani, Roberta Inorganica Chimica Acta, Vol. 101, Issue 3 https://doi.org/10.1016/S0020-1693(00)87650-1	journal	July 1985
Protonation and methylation reactions of 2-pyridyl-palladium(II) and -platinum(II) complexes Crociani, Bruno; di Bianca, Francesca; Giovenco, Amalia Journal of Organometallic Chemistry, Vol. 251, Issue 3 https://doi.org/10.1016/S0022-328X(00)98785-0	journal	August 1983
Organometallic nucleophiles. A mechanistic study of halide displacement at saturated carbon by 2- and 4-pyridyl complexes of palladium(II) and platinum(II) Canovese, L.; Visentin, F.; Uguagliati, P. Journal of Organometallic Chemistry, Vol. 525, Issue 1-2 https://doi.org/10.1016/S0022-328X(96)06490-X	journal	November 1996
A novel functionalized P,C,P pincer ligand complex Grimm, Jost C.; Nachtigal, Christiane; Mack, H. -G Inorganic Chemistry Communications, Vol. 3, Issue 10 https://doi.org/10.1016/S1387-7003(00)00132-5	journal	October 2000
Alkane dehydrogenation reactions catalyzed by pincer-metal complexes Das, Kanu; Kumar, Akshai Advances in Organometallic Chemistry, Vol. 72, p. 1-57 https://doi.org/10.1016/bs.adomc.2019.02.004	book	January 2019
Electrochemistry of transition metal complex catalysts Novak, Filip; Speiser, Bernd; Mohammad, Hani A. Y. Electrochimica Acta, Vol. 49, Issue 22-23 https://doi.org/10.1016/j.electacta.2003.11.038	journal	September 2004
pKa values in organic chemistry – Making maximum use of the available data Kütt, Agnes; Selberg, Sigrid; Kaljurand, Ivari Tetrahedron Letters, Vol. 59, Issue 42 https://doi.org/10.1016/j.tetlet.2018.08.054	journal	October 2018
Lactate Racemase Nickel-Pincer Cofactor Operates by a Proton-Coupled Hydride Transfer Mechanism Rankin, Joel A.; Mauban, Robert C.; Fellner, Matthias Biochemistry, Vol. 57, Issue 23 https://doi.org/10.1021/acs.biochem.8b00100	journal	February 2018
Dehydrogenation of Alkanes and Aliphatic Groups by Pincer-Ligated Metal Complexes Kumar, Akshai; Bhatti, Tariq M.; Goldman, Alan S. Chemical Reviews, Vol. 117, Issue 19 https://doi.org/10.1021/acs.chemrev.7b00247	journal	September 2017
Mesoionic and Related Less Heteroatom-Stabilized N-Heterocyclic Carbene Complexes: Synthesis, Catalysis, and Other Applications Vivancos, Ángela; Segarra, Candela; Albrecht, Martin Chemical Reviews, Vol. 118, Issue 19 https://doi.org/10.1021/acs.chemrev.8b00148	journal	March 2018
Synthesis and Characterization of 3,5-Bis(di-tert-butylphosphinito)pyridine Pincer Complexes Swisher, Nicholas A.; Grubbs, Robert H. Organometallics, Vol. 39, Issue 13 https://doi.org/10.1021/acs.organomet.0c00270	journal	July 2020
Comparing Square-Planar Rh^I and Ir^I: Metal–Ligand Proton Tautomerism, Fluxionality, and Reactivity Jain, Anant Kumar; Gau, Michael R.; Carroll, Patrick J. Organometallics, Vol. 41, Issue 22 https://doi.org/10.1021/acs.organomet.2c00302	journal	September 2022
Tuning of Metal Complex Electronics and Reactivity by Remote Lewis Acid Binding to π-Coordinated Pyridine Diphosphine Ligands Horak, Kyle T.; VanderVelde, David G.; Agapie, Theodor Organometallics, Vol. 34, Issue 19 https://doi.org/10.1021/acs.organomet.5b00562	journal	August 2015
Catalytic Dehydrogenation of Alkanes by PCP–Pincer Iridium Complexes Using Proton and Electron Acceptors Shada, Arun Dixith Reddy; Miller, Alexander J. M.; Emge, Thomas J. ACS Catalysis, Vol. 11, Issue 5 https://doi.org/10.1021/acscatal.0c05160	journal	February 2021
Alkane Dehydrogenation Catalyzed by a Fluorinated Phebox Iridium Complex Zhou, Xiaoguang; Malakar, Santanu; Dugan, Thomas ACS Catalysis, Vol. 11, Issue 22 https://doi.org/10.1021/acscatal.1c03562	journal	November 2021
Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M. Chemical Reviews, Vol. 110, Issue 12 https://doi.org/10.1021/cr100085k	journal	December 2010
Beyond Conventional N -Heterocyclic Carbenes: Abnormal, Remote, and Other Classes of NHC Ligands with Reduced Heteroatom Stabilization Schuster, Oliver; Yang, Liangru; Raubenheimer, Helgard G. Chemical Reviews, Vol. 109, Issue 8 https://doi.org/10.1021/cr8005087	journal	August 2009
Chemical Redox Agents for Organometallic Chemistry Connelly, Neil G.; Geiger, William E. Chemical Reviews, Vol. 96, Issue 2 https://doi.org/10.1021/cr940053x	journal	January 1996
Palladium-hydrogen-phosphorus bridging in a palladium(I) dimer Albinati, A.; Lianza, F.; Pasquali, M. Inorganic Chemistry, Vol. 30, Issue 25 https://doi.org/10.1021/ic00025a004	journal	December 1991
[Ni(Et ₂ PCH ₂ NMeCH ₂ PEt ₂ ) ₂ ] ²⁺ as a Functional Model for Hydrogenases Curtis, Calvin J.; Miedaner, Alex; Ciancanelli, Rebecca Inorganic Chemistry, Vol. 42, Issue 1 https://doi.org/10.1021/ic020610v	journal	January 2003
Kinetics and thermodynamics of intra- and intermolecular carbon-hydrogen bond activation Jones, William D.; Feher, Frank J. Journal of the American Chemical Society, Vol. 107, Issue 3 https://doi.org/10.1021/ja00289a014	journal	February 1985
Mechanism of hydrogenolysis of dineopentylbis(triethylphosphine)platinum(II) Reamey, Robert H.; Whitesides, George M. Journal of the American Chemical Society, Vol. 106, Issue 1 https://doi.org/10.1021/ja00313a018	journal	January 1984
Experimental and Computational Studies on the Mechanism of N-Heterocycle C−H Activation by Rh(I) Wiedemann, Sean H.; Lewis, Jared C.; Ellman, Jonathan A. Journal of the American Chemical Society, Vol. 128, Issue 7 https://doi.org/10.1021/ja0576684	journal	January 2006
Iridium(III)-Induced Isomerization of 2-Substituted Pyridines to N-Heterocyclic Carbenes Alvarez, Eleuterio; Conejero, Salvador; Paneque, Margarita Journal of the American Chemical Society, Vol. 128, Issue 40 https://doi.org/10.1021/ja0646592	journal	September 2006
Stabilization of NH Tautomers of Quinolines by Osmium and Ruthenium Esteruelas, Miguel A.; Fernández-Alvarez, Francisco J.; Oñate, Enrique Journal of the American Chemical Society, Vol. 128, Issue 40 https://doi.org/10.1021/ja064979l	journal	September 2006
Rh(I)-Catalyzed Alkylation of Quinolines and Pyridines via C−H Bond Activation Lewis, Jared C.; Bergman, Robert G.; Ellman, Jonathan A. Journal of the American Chemical Society, Vol. 129, Issue 17 https://doi.org/10.1021/ja070388z	journal	April 2007
Rh(I)-Catalyzed Arylation of Heterocycles via C−H Bond Activation: Expanded Scope through Mechanistic Insight Lewis, Jared C.; Berman, Ashley M.; Bergman, Robert G. Journal of the American Chemical Society, Vol. 130, Issue 8 https://doi.org/10.1021/ja0748985	journal	February 2008
Rearrangement of Pyridine to Its 2-Carbene Tautomer Mediated by Iridium Álvarez, Eleuterio; Conejero, Salvador; Lara, Patricia Journal of the American Chemical Society, Vol. 129, Issue 46 https://doi.org/10.1021/ja075685i	journal	October 2007
Cleavage of Ether, Ester, and Tosylate C(sp ³ )–O Bonds by an Iridium Complex, Initiated by Oxidative Addition of C–H Bonds. Experimental and Computational Studies Kundu, Sabuj; Choi, Jongwook; Wang, David Y. Journal of the American Chemical Society, Vol. 135, Issue 13 https://doi.org/10.1021/ja312464b	journal	March 2013
Estimating the Acidity of Transition Metal Hydride and Dihydrogen Complexes by Adding Ligand Acidity Constants Morris, Robert H. Journal of the American Chemical Society, Vol. 136, Issue 5 https://doi.org/10.1021/ja410718r	journal	January 2014
Trends in Ground-State Entropies for Transition Metal Based Hydrogen Atom Transfer Reactions Mader, Elizabeth A.; Manner, Virginia W.; Markle, Todd F. Journal of the American Chemical Society, Vol. 131, Issue 12 https://doi.org/10.1021/ja8081846	journal	April 2009
Metal/Ligand Proton Tautomerism Facilitates Dinuclear H ₂ Reductive Elimination Kuo, Jonathan L.; Goldberg, Karen I. Journal of the American Chemical Society, Vol. 142, Issue 51 https://doi.org/10.1021/jacs.0c10458	journal	December 2020
Reactivity of Iridium Complexes of a Triphosphorus-Pincer Ligand Based on a Secondary Phosphine. Catalytic Alkane Dehydrogenation and the Origin of Extremely High Activity Gordon, Benjamin M.; Lease, Nicholas; Emge, Thomas J. Journal of the American Chemical Society, Vol. 144, Issue 9 https://doi.org/10.1021/jacs.1c13309	journal	February 2022
Pyridine-Based PCP-Ruthenium Complexes: Unusual Structures and Metal–Ligand Cooperation Tang, Shan; von Wolff, Niklas; Diskin-Posner, Yael Journal of the American Chemical Society, Vol. 141, Issue 18 https://doi.org/10.1021/jacs.9b02669	journal	April 2019
Chemistry of phosphido-bridged palladium(I) dimers. .eta.2-Pd-H-P interactions: a new bonding mode for secondary phosphines Leoni, Piero; Pasquali, Marco; Sommovigo, Milena Organometallics, Vol. 12, Issue 5 https://doi.org/10.1021/om00029a031	journal	May 1993
C−H Oxidative Addition with a (PCP)Ir(III)-Pincer Complex Mohammad, Hani A. Y.; Grimm, Jost C.; Eichele, Klaus Organometallics, Vol. 21, Issue 26 https://doi.org/10.1021/om020621w	journal	December 2002
Synthesis and Reactivity of a Coordinatively Unsaturated Ruthenium(II) Parent Amido Complex: Studies of X−H Activation (X = H or C) Conner, David; Jayaprakash, K. N.; Cundari, Thomas R. Organometallics, Vol. 23, Issue 11 https://doi.org/10.1021/om049836r	journal	April 2004
A Highly Stable Adamantyl-Substituted Pincer-Ligated Iridium Catalyst for Alkane Dehydrogenation Punji, Benudhar; Emge, Thomas J.; Goldman, Alan S. Organometallics, Vol. 29, Issue 12 https://doi.org/10.1021/om100145q	journal	May 2010
Rhodium and Iridium Complexes with Chelating C–C′-Imidazolylidene–Pyridylidene Ligands: Systematic Approach to Normal, Abnormal, and Remote Coordination Modes Segarra, Candela; Mas-Marzá, Elena; Mata, José A. Organometallics, Vol. 31, Issue 14 https://doi.org/10.1021/om3005096	journal	July 2012
Alkenylation of 2-Methylpyridine via Pyridylidene–Osmium Complexes Bajo, Sonia; Esteruelas, Miguel A.; López, Ana M. Organometallics, Vol. 31, Issue 24 https://doi.org/10.1021/om301058n	journal	December 2012
Osmium and Ruthenium Complexes Containing an N-Heterocyclic Carbene Ligand Derived from Benzo[h]quinoline Esteruelas, Miguel A.; Fernández-Alvarez, Francisco J.; Oñate, Enrique Organometallics, Vol. 26, Issue 21 https://doi.org/10.1021/om700639a	journal	September 2007
C_β(sp²)−H Bond Activation of α,β-Unsaturated Ketones Promoted by a Hydride-Elongated Dihydrogen Complex: Formation of Osmafuran Derivatives with Carbene, Carbyne, and NH-Tautomerized α-Substituted Pyridine Ligands Buil, María L.; Esteruelas, Miguel A.; Garcés, Karin Organometallics, Vol. 27, Issue 18 https://doi.org/10.1021/om800439g	journal	August 2008
NH-Tautomerization of Quinolines and 2-Methylpyridine Promoted by a Hydride-Iridium(III) Complex: Importance of the Hydride Ligand Esteruelas, Miguel A.; Fernández-Alvarez, Francisco J.; Oliván, Montserrat Organometallics, Vol. 28, Issue 7 https://doi.org/10.1021/om8011954	journal	February 2009
A first structural and theoretical comparison of pyridinylidene-type rNHC (remote N-heterocyclic carbene) and NHC complexes of Ni(ii) obtained by oxidative substitution Schneider, Sabine K.; Julius, Gerrit R.; Loschen, Christoph Dalton Trans., Issue 9 https://doi.org/10.1039/B512419K	journal	January 2006
The first crystal structure of a monomeric phenoxyl radical: 2,4,6-tri-tert-butylphenoxyl radical Manner, Virginia W.; Markle, Todd F.; Freudenthal, John H. Chem. Commun., Issue 2 https://doi.org/10.1039/B712872J	journal	January 2008
A bio-inspired design and computational prediction of scorpion-like SCS nickel pincer complexes for lactate racemization Qiu, Bing; Yang, Xinzheng Chem. Commun., Vol. 53, Issue 83 https://doi.org/10.1039/C7CC06416K	journal	January 2017
The underappreciated influence of ancillary halide on metal–ligand proton tautomerism Jain, Anant Kumar; Gau, Michael R.; Carroll, Patrick J. Chemical Science, Vol. 13, Issue 26 https://doi.org/10.1039/D2SC00279E	journal	January 2022
Transition metal–carbon bonds. Part XLII. Complexes of nickel, palladium, platinum, rhodium and iridium with the tridentate ligand 2,6-bis[(di-t-butylphosphino)methyl]phenyl Moulton, Christopher J.; Shaw, Bernard L. J. Chem. Soc., Dalton Trans., Issue 11 https://doi.org/10.1039/DT9760001020	journal	January 1976
Reactions of iridium hydride pincer complexes with dioxygen: new dioxygen complexes and reversible O2 binding Bridget Williams, D.; Kaminsky, Werner; Mayer, James M. Chemical Communications, Issue 35 https://doi.org/10.1039/b802739k	journal	January 2008
Iridium complexes bearing a PNP ligand, favoring facile C(sp3)–H bond cleavage Lokare, Kapil S.; Nielsen, Robert J.; Yousufuddin, Muhammed Dalton Transactions, Vol. 40, Issue 36 https://doi.org/10.1039/c1dt10577a	journal	January 2011
Cleavage of dinitrogen to yield a (t-BuPOCOP)molybdenum(iv) nitride Hebden, Travis J.; Schrock, Richard R.; Takase, Michael K. Chemical Communications, Vol. 48, Issue 13 https://doi.org/10.1039/c2cc17634c	journal	January 2012
Carbene complexes of iridium, rhodium, manganese, chromium, and iron containing thiazolidinylidene and pyridinylidene ligands Fraser, Paul J.; Roper, Warren R.; Stone, F. Gordon A. Journal of the Chemical Society, Dalton Transactions, Issue 7 https://doi.org/10.1039/dt9740000760	journal	January 1974
Agostic interactions in transition metal compounds Brookhart, M.; Green, M. L. H.; Parkin, G. Proceedings of the National Academy of Sciences, Vol. 104, Issue 17 https://doi.org/10.1073/pnas.0610747104	journal	April 2007
Nickel pincer model of the active site of lactate racemase involves ligand participation in hydride transfer Xu, Tao; Wodrich, Matthew D.; Scopelliti, Rosario Proceedings of the National Academy of Sciences, Vol. 114, Issue 6 https://doi.org/10.1073/pnas.1616038114	journal	January 2017
A tethered niacin-derived pincer complex with a nickel-carbon bond in lactate racemase Desguin, Benoît; Zhang, Tuo; Soumillion, Patrice Science, Vol. 349, Issue 6243 https://doi.org/10.1126/science.aab2272	journal	July 2015
Comparative Studies of 2-, 3-, and 4-Pyridylpalladium(II) Complexes: Synthesis and Properties Isobe, Kiyoshi; Nakamura, Yukio; Miwa, Toshio Bulletin of the Chemical Society of Japan, Vol. 60, Issue 1 https://doi.org/10.1246/bcsj.60.149	journal	January 1987

Metal–Ligand Proton Tautomerism, Electron Transfer, and C(sp ³ )–H Activation by a 4-Pyridinyl-Pincer Iridium Hydride Complex

References (69)

Similar Records

Related Subjects

Metal–Ligand Proton Tautomerism, Electron Transfer, and C(sp 3 )–H Activation by a 4-Pyridinyl-Pincer Iridium Hydride Complex

Citation Formats

References (69)

Similar Records

Related Subjects

Metal–Ligand Proton Tautomerism, Electron Transfer, and C(sp ³ )–H Activation by a 4-Pyridinyl-Pincer Iridium Hydride Complex