Control of Catalyst Isomers Using an N-Phenyl-Substituted RN(CH2CH2PiPr2)2 Pincer Ligand in CO2 Hydrogenation and Formic Acid Dehydrogenation

Curley, Julia B.; Hert, Clayton; Bernskoetter, Wesley H.; Hazari, Nilay; Mercado, Brandon Q.

doi:10.1021/acs.inorgchem.1c03372

Title: Control of Catalyst Isomers Using an N-Phenyl-Substituted RN(CH₂CH₂PⁱPr₂)₂ Pincer Ligand in CO₂ Hydrogenation and Formic Acid Dehydrogenation

Journal Article · Sat Dec 25 00:00:00 EST 2021 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.1c03372· OSTI ID:1839397

Curley, Julia B. ^[1]; Hert, Clayton ^[2];

^[2];

^[1]; Mercado, Brandon Q. ^[1]

Yale Univ., New Haven, CT (United States)
Univ. of Missouri, Columbia, MO (United States)

A novel pincer ligand, ^{i Pr}PN^PhP [PhN- (CH₂CH₂PⁱPr₂)₂], which is an analogue of the versatile MACHO ligand, ^iPrPN^HP [HN(CH₂CH₂PⁱPr₂)₂], was synthesized and characterized. The ligand was coordinated to ruthenium, and a series of hydride-containing complexes were isolated and characterized by NMR and IR spectroscopies, as well as X-ray diffraction. Comparisons to previously published analogues ligated by ^iPrPN^HP and ^iPrPN^MeP [CH₃N(CH₂CH₂PⁱPr₂)₂] illustrate that there are large changes in the coordination chemistry that occur when the nitrogen substituent of the pincer ligand is altered. For example, ruthenium hydrides supported by the ^iPrPN^PhP ligand always form the syn isomer (where syn/anti refer to the relative orientation of the group on nitrogen and the hydride ligand on ruthenium), whereas complexes supported by ^iPrPN^HP form the anti isomer and complexes supported by ^iPrPN^MeP form a mixture of syn and anti isomers. We evaluated the impact of the nitrogen substituent of the pincer ligand in catalysis by comparing a series of ^iPrPN^RP (R = H, Me, Ph)-ligated ruthenium hydride complexes as catalysts for formic acid dehydrogenation and carbon dioxide (CO₂) hydrogenation to formate. The ^iPrPN^PhP-ligated species is the most active for formic acid dehydrogenation, and mechanistic studies suggest that this is likely because there are kinetic advantages for catalysts that operate via the syn isomer. In CO₂ hydrogenation, the ^iPrPN^PhP-ligated species is again the most active under our optimal conditions, and we report some of the highest turnover frequencies for homogeneous catalysts. Experimental and theoretical insights into the turnover-limiting step of catalysis provide a basis for the observed trends in catalytic activity. Additionally, the stability of our complexes enabled us to detect a previously unobserved autocatalytic effect involving the base that is added to drive the reaction. Overall, by modifying the nitrogen substituent on the MACHO ligand, we have developed highly active catalysts for formic acid dehydrogenation and CO₂ hydrogenation and also provided a framework for future catalyst development.

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Research Organization:: Yale Univ., New Haven, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0018222

OSTI ID:: 1839397

Journal Information:: Inorganic Chemistry, Vol. 61, Issue 1; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (95)

Synthesis and characterization of rhenium( iii ) complexes with (Ph ₂ PCH ₂ CH ₂ ) ₂ NR diphosphinoamine ligands Salvarese, Nicola; Refosco, Fiorenzo; Seraglia, Roberta Dalton Transactions, Vol. 46, Issue 28 https://doi.org/10.1039/C7DT01032J	journal	January 2017
Cobalt Pincer Complexes for Catalytic Reduction of Carboxylic Acid Esters Junge, Kathrin; Wendt, Bianca; Cingolani, Andrea Chemistry - A European Journal, Vol. 24, Issue 5 https://doi.org/10.1002/chem.201705201	journal	December 2017
Additive‐Free Formic Acid Dehydrogenation Using a Pincer‐Supported Iron Catalyst Curley, Julia B.; Bernskoetter, Wesley H.; Hazari, Nilay ChemCatChem, Vol. 12, Issue 7 https://doi.org/10.1002/cctc.202000066	journal	February 2020
Cobalt‐Catalyzed Aqueous Dehydrogenation of Formic Acid Zhou, Wei; Wei, Zhihong; Spannenberg, Anke Chemistry – A European Journal, Vol. 25, Issue 36 https://doi.org/10.1002/chem.201805612	journal	May 2019
Alcohol-Assisted Hydrogenation of Carbon Monoxide to Methanol Using Molecular Manganese Catalysts Kaithal, Akash; Werlé, Christophe; Leitner, Walter JACS Au, Vol. 1, Issue 2 https://doi.org/10.1021/jacsau.0c00091	journal	January 2021
Mechanism of CO ₂ hydrogenation to formates by homogeneous Ru-PNP pincer catalyst: from a theoretical description to performance optimization Filonenko, Georgy A.; Hensen, Emiel J. M.; Pidko, Evgeny A. Catal. Sci. Technol., Vol. 4, Issue 10 https://doi.org/10.1039/C4CY00568F	journal	January 2014
First-Row Transition Metal (De)Hydrogenation Catalysis Based On Functional Pincer Ligands Alig, Lukas; Fritz, Maximilian; Schneider, Sven Chemical Reviews, Vol. 119, Issue 4 https://doi.org/10.1021/acs.chemrev.8b00555	journal	October 2018
Carbon Dioxide Insertion into Group 9 and 10 Metal–Element σ Bonds Hazari, Nilay; Heimann, Jessica E. Inorganic Chemistry, Vol. 56, Issue 22 https://doi.org/10.1021/acs.inorgchem.7b02315	journal	November 2017
Metal-Ligand Cooperation Khusnutdinova, Julia R.; Milstein, David Angewandte Chemie International Edition, Vol. 54, Issue 42 https://doi.org/10.1002/anie.201503873	journal	September 2015
A prolific catalyst for dehydrogenation of neat formic acid Celaje, Jeff Joseph A.; Lu, Zhiyao; Kedzie, Elyse A. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11308	journal	April 2016
Secondary Coordination Sphere Interactions Facilitate the Insertion Step in an Iridium(III) CO ₂ Reduction Catalyst Schmeier, Timothy J.; Dobereiner, Graham E.; Crabtree, Robert H. Journal of the American Chemical Society, Vol. 133, Issue 24 https://doi.org/10.1021/ja2035514	journal	June 2011
Molecularly Defined Manganese Catalyst for Low-Temperature Hydrogenation of Carbon Monoxide to Methanol Ryabchuk, Pavel; Stier, Kenta; Junge, Kathrin Journal of the American Chemical Society, Vol. 141, Issue 42 https://doi.org/10.1021/jacs.9b08990	journal	September 2019
Highly Efficient Reversible Hydrogenation of Carbon Dioxide to Formates Using a Ruthenium PNP-Pincer Catalyst Filonenko, Georgy A.; van Putten, Robbert; Schulpen, Erik N. ChemCatChem, Vol. 6, Issue 6 https://doi.org/10.1002/cctc.201402119	journal	April 2014
Efficient and Mild Carbon Dioxide Hydrogenation to Formate Catalyzed by Fe(II) Hydrido Carbonyl Complexes Bearing 2,6-(Diaminopyridyl)diphosphine Pincer Ligands Bertini, Federica; Gorgas, Nikolaus; Stöger, Berthold ACS Catalysis, Vol. 6, Issue 5 https://doi.org/10.1021/acscatal.6b00416	journal	April 2016
Reversible hydrogen storage using CO₂ and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures Hull, Jonathan F.; Himeda, Yuichiro; Wang, Wan-Hui Nature Chemistry, Vol. 4, Issue 5, p. 383-388 https://doi.org/10.1038/nchem.1295	journal	March 2012
Efficient H ₂ generation from formic acid using azole complexes in water Manaka, Yuichi; Wang, Wan-Hui; Suna, Yuki Catal. Sci. Technol., Vol. 4, Issue 1 https://doi.org/10.1039/C3CY00830D	journal	January 2014
Review: Pincer ligands—Tunable, versatile and applicable Lawrence, Mark A. W.; Green, Kerry-Ann; Nelson, Peter N. Polyhedron, Vol. 143 https://doi.org/10.1016/j.poly.2017.08.017	journal	March 2018
Hydrogenation of Esters to Alcohols with a Well-Defined Iron Complex Werkmeister, Svenja; Junge, Kathrin; Wendt, Bianca Angewandte Chemie International Edition, Vol. 53, Issue 33 https://doi.org/10.1002/anie.201402542	journal	May 2014
Selective Iron-Catalyzed N -Formylation of Amines using Dihydrogen and Carbon Dioxide Jayarathne, Upul; Hazari, Nilay; Bernskoetter, Wesley H. ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03834	journal	January 2018
Iron-Catalyzed Amide Formation from the Dehydrogenative Coupling of Alcohols and Secondary Amines Lane, Elizabeth M.; Uttley, Katherine B.; Hazari, Nilay Organometallics, Vol. 36, Issue 10 https://doi.org/10.1021/acs.organomet.7b00258	journal	May 2017
Ligand-Controlled Cobalt-Catalyzed Transfer Hydrogenation of Alkynes: Stereodivergent Synthesis of Z - and E- Alkenes Fu, Shaomin; Chen, Nan-Yu; Liu, Xufang Journal of the American Chemical Society, Vol. 138, Issue 27 https://doi.org/10.1021/jacs.6b04271	journal	June 2016
A Family of Active Iridium Catalysts for Transfer Hydrogenation of Ketones Clarke, Zaheer E.; Maragh, Paul T.; Dasgupta, Tara P. Organometallics, Vol. 25, Issue 17 https://doi.org/10.1021/om060049z	journal	August 2006
Cobalt aminodiphosphine complexes as catalysts in the oxidation of n-octane Naicker, Dunesha; Friedrich, Holger B.; Omondi, Bernard RSC Advances, Vol. 5, Issue 77 https://doi.org/10.1039/C5RA07365K	journal	January 2015
Efficient Reversible Hydrogen Carrier System Based on Amine Reforming of Methanol Kothandaraman, Jotheeswari; Kar, Sayan; Sen, Raktim Journal of the American Chemical Society, Vol. 139, Issue 7 https://doi.org/10.1021/jacs.6b11637	journal	February 2017
Highly efficient additive-free dehydrogenation of neat formic acid Kar, Sayan; Rauch, Michael; Leitus, Gregory Nature Catalysis, Vol. 4, Issue 3 https://doi.org/10.1038/s41929-021-00575-4	journal	February 2021
Cooperative Aliphatic PNP Amido Pincer Ligands - Versatile Building Blocks for Coordination Chemistry and Catalysis Schneider, Sven; Meiners, Jenni; Askevold, Bjorn European Journal of Inorganic Chemistry, Vol. 2012, Issue 3 https://doi.org/10.1002/ejic.201100880	journal	November 2011
Highly Efficient Ruthenium-Catalyzed N-Formylation of Amines with H ₂ and CO ₂ Zhang, Lei; Han, Zhaobin; Zhao, Xiaoyu Angewandte Chemie International Edition, Vol. 54, Issue 21 https://doi.org/10.1002/anie.201500939	journal	April 2015
Selective conversion of glycerol to lactic acid with iron pincer precatalysts Sharninghausen, Liam S.; Mercado, Brandon Q.; Crabtree, Robert H. Chemical Communications, Vol. 51, Issue 90 https://doi.org/10.1039/C5CC06857F	journal	January 2015
Cobalt-catalyzed transfer hydrogenation of CO and CN bonds Zhang, Guoqi; Hanson, Susan K. Chemical Communications, Vol. 49, Issue 86 https://doi.org/10.1039/c3cc45900d	journal	January 2013
Catalytic Hydrogenation of Esters. Development of an Efficient Catalyst and Processes for Synthesising ( R )-1,2-Propanediol and 2-( l -Menthoxy)ethanol Kuriyama, Wataru; Matsumoto, Takaji; Ogata, Osamu Organic Process Research & Development, Vol. 16, Issue 1 https://doi.org/10.1021/op200234j	journal	November 2011
Bond Activation and Catalysis by Ruthenium Pincer Complexes Gunanathan, Chidambaram; Milstein, David Chemical Reviews, Vol. 114, Issue 24 https://doi.org/10.1021/cr5002782	journal	November 2014
Ruthenium-catalyzed hydrogen generation from glycerol and selective synthesis of lactic acid Li, Yang; Nielsen, Martin; Li, Bin Green Chemistry, Vol. 17, Issue 1 https://doi.org/10.1039/C4GC01707B	journal	January 2015
Unravelling the Mechanism of Basic Aqueous Methanol Dehydrogenation Catalyzed by Ru–PNP Pincer Complexes Alberico, Elisabetta; Lennox, Alastair J. J.; Vogt, Lydia K. Journal of the American Chemical Society, Vol. 138, Issue 45 https://doi.org/10.1021/jacs.6b05692	journal	November 2016
Improved Second Generation Iron Pincer Complexes for Effective Ester Hydrogenation Elangovan, Saravanakumar; Wendt, Bianca; Topf, Christoph Advanced Synthesis & Catalysis, Vol. 358, Issue 5 https://doi.org/10.1002/adsc.201500930	journal	January 2016
The Role of Proton Shuttles in the Reversible Activation of Hydrogen via Metal–Ligand Cooperation Smith, Nicholas E.; Bernskoetter, Wesley H.; Hazari, Nilay Journal of the American Chemical Society, Vol. 141, Issue 43 https://doi.org/10.1021/jacs.9b09062	journal	October 2019
Ruthenium-Catalyzed Urea Synthesis Using Methanol as the C1 Source Kim, Seung Hyo; Hong, Soon Hyeok Organic Letters, Vol. 18, Issue 2 https://doi.org/10.1021/acs.orglett.5b03328	journal	December 2015
Amide versus amine ligand paradigm in the direct amination of alcohols with Ru-PNP complexes Pingen, Dennis; Choi, Jong-Hoo; Allen, Henry Catalysis Science & Technology, Vol. 8, Issue 15 https://doi.org/10.1039/C8CY00869H	journal	January 2018
Chemoselective semihydrogenation of alkynes catalyzed by manganese( i )-PNP pincer complexes Garbe, Marcel; Budweg, Svenja; Papa, Veronica Catalysis Science & Technology, Vol. 10, Issue 12 https://doi.org/10.1039/D0CY00992J	journal	January 2020
Breakthroughs in Hydrogen Storage-Formic Acid as a Sustainable Storage Material for Hydrogen Joó, Ferenc ChemSusChem, Vol. 1, Issue 10 https://doi.org/10.1002/cssc.200800133	journal	October 2008
Hydrogen Generation at Ambient Conditions: Application in Fuel Cells Boddien, Albert; Loges, Björn; Junge, Henrik ChemSusChem, Vol. 1, Issue 8-9 https://doi.org/10.1002/cssc.200800093	journal	September 2008
Contrasting reactivity behaviour of the [RuHCl(CO)(PNP)] complex with electrophilic reagents XOTf (X = H, CH ₃ , Me ₃ Si) Ramaraj, A.; Nethaji, Munirathinam; Jagirdar, Balaji R. Dalton Trans., Vol. 43, Issue 39 https://doi.org/10.1039/C4DT01570C	journal	January 2014
Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide Nielsen, Martin; Alberico, Elisabetta; Baumann, Wolfgang Nature, Vol. 495, Issue 7439 https://doi.org/10.1038/nature11891	journal	February 2013
Iron-Catalyzed Hydrogenation of Amides to Alcohols and Amines Rezayee, Nomaan M.; Samblanet, Danielle C.; Sanford, Melanie S. ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01454	journal	August 2016
Osmium and Ruthenium Catalysts for Dehydrogenation of Alcohols Bertoli, Marcello; Choualeb, Aldjia; Lough, Alan J. Organometallics, Vol. 30, Issue 13 https://doi.org/10.1021/om200437n	journal	July 2011
Additive-Free Cobalt-Catalyzed Hydrogenation of Esters to Alcohols Yuwen, Jing; Chakraborty, Sumit; Brennessel, William W. ACS Catalysis, Vol. 7, Issue 5 https://doi.org/10.1021/acscatal.7b00623	journal	April 2017
Understanding the Mechanisms of Cobalt-Catalyzed Hydrogenation and Dehydrogenation Reactions Zhang, Guoqi; Vasudevan, Kalyan V.; Scott, Brian L. Journal of the American Chemical Society, Vol. 135, Issue 23 https://doi.org/10.1021/ja402679a	journal	May 2013
Homogeneous Catalysis for Sustainable Hydrogen Storage in Formic Acid and Alcohols Sordakis, Katerina; Tang, Conghui; Vogt, Lydia K. Chemical Reviews, Vol. 118, Issue 2 https://doi.org/10.1021/acs.chemrev.7b00182	journal	October 2017
Base-Free Methanol Dehydrogenation Using a Pincer-Supported Iron Compound and Lewis Acid Co-catalyst Bielinski, Elizabeth A.; Förster, Moritz; Zhang, Yuanyuan ACS Catalysis, Vol. 5, Issue 4 https://doi.org/10.1021/acscatal.5b00137	journal	March 2015
Mechanistic Insights into Ruthenium-Pincer-Catalyzed Amine-Assisted Homogeneous Hydrogenation of CO 2 to Methanol Kar, Sayan; Sen, Raktim; Kothandaraman, Jotheeswari Journal of the American Chemical Society, Vol. 141, Issue 7 https://doi.org/10.1021/jacs.8b12763	journal	February 2019
Catalytic Solvolysis of Ammonia Borane Graham, Todd W.; Tsang, Chi-Wing; Chen, Xuanhua Angewandte Chemie International Edition, Vol. 49, Issue 46 https://doi.org/10.1002/anie.201003074	journal	October 2010
Iridium-Catalyzed Hydrogenation of Carboxylic Acid Esters Junge, Kathrin; Wendt, Bianca; Jiao, Haijun ChemCatChem, Vol. 6, Issue 10 https://doi.org/10.1002/cctc.201402421	journal	September 2014
Lewis Acid-Assisted Formic Acid Dehydrogenation Using a Pincer-Supported Iron Catalyst Bielinski, Elizabeth A.; Lagaditis, Paraskevi O.; Zhang, Yuanyuan Journal of the American Chemical Society, Vol. 136, Issue 29 https://doi.org/10.1021/ja505241x	journal	July 2014
Selective Iron-Catalyzed Deaminative Hydrogenation of Amides Jayarathne, Upul; Zhang, Yuanyuan; Hazari, Nilay Organometallics, Vol. 36, Issue 2 https://doi.org/10.1021/acs.organomet.6b00816	journal	January 2017
Synthesis, characterization and theoretical investigations of molybdenum carbonyl complexes with phosphorus/nitrogen/phosphorus ligand as bidentate and tridentate modes Goren Keskin, Seyma; Stanley, Julie M.; Cowley, Alan H. Polyhedron, Vol. 138 https://doi.org/10.1016/j.poly.2017.09.037	journal	December 2017
Hydrogenation of Esters to Alcohols Catalyzed by Defined Manganese Pincer Complexes Elangovan, Saravanakumar; Garbe, Marcel; Jiao, Haijun Angewandte Chemie International Edition, Vol. 55, Issue 49 https://doi.org/10.1002/anie.201607233	journal	September 2016
Unprecedentedly High Formic Acid Dehydrogenation Activity on an Iridium Complex with an N , N ′-Diimine Ligand in Water Wang, Zhijun; Lu, Sheng-Mei; Li, Jun Chemistry - A European Journal, Vol. 21, Issue 36 https://doi.org/10.1002/chem.201502086	journal	July 2015
Sequential Hydrogenation of CO ₂ to Methanol Using a Pincer Iron Catalyst Lane, Elizabeth M.; Zhang, Yuanyuan; Hazari, Nilay Organometallics, Vol. 38, Issue 15 https://doi.org/10.1021/acs.organomet.9b00413	journal	July 2019
Hydrogenation of CO2, carbonyl and imine substrates catalyzed by [IrH3(PhPNHP)] complex Ramaraj, Ayyappan; Nethaji, Munirathinam; Jagirdar, Balaji R. Journal of Organometallic Chemistry, Vol. 883 https://doi.org/10.1016/j.jorganchem.2018.12.017	journal	March 2019
Long-range metal–ligand bifunctional catalysis: cyclometallated iridium catalysts for the mild and rapid dehydrogenation of formic acid Barnard, Jonathan H.; Wang, Chao; Berry, Neil G. Chemical Science, Vol. 4, Issue 3 https://doi.org/10.1039/c2sc21923a	journal	January 2013
Selective Hydrogenation of Amides to Amines and Alcohols Catalyzed by Improved Iron Pincer Complexes Schneck, Felix; Assmann, Maik; Balmer, Markus Organometallics, Vol. 35, Issue 11 https://doi.org/10.1021/acs.organomet.6b00251	journal	May 2016
Tandem Amine and Ruthenium-Catalyzed Hydrogenation of CO ₂ to Methanol Rezayee, Nomaan M.; Huff, Chelsea A.; Sanford, Melanie S. Journal of the American Chemical Society, Vol. 137, Issue 3 https://doi.org/10.1021/ja511329m	journal	January 2015
Iridium-PNP Pincer Complexes for Methanol Dehydrogenation at Low Base Concentration Prichatz, Christoph; Alberico, Elisabetta; Baumann, Wolfgang ChemCatChem, Vol. 9, Issue 11 https://doi.org/10.1002/cctc.201700015	journal	May 2017
Effective Pincer Cobalt Precatalysts for Lewis Acid Assisted CO ₂ Hydrogenation Spentzos, Ariana Z.; Barnes, Charles L.; Bernskoetter, Wesley H. Inorganic Chemistry, Vol. 55, Issue 16 https://doi.org/10.1021/acs.inorgchem.6b01454	journal	July 2016
Catalytic Cross-Coupling of Secondary Alcohols Thiyagarajan, Subramanian; Gunanathan, Chidambaram Journal of the American Chemical Society, Vol. 141, Issue 9 https://doi.org/10.1021/jacs.9b00025	journal	February 2019
Synthesis, characterization, coordination chemistry, and luminescence studies of copper, silver, palladium, and platinum complexes with a phosphorus/nitrogen/phosphorus ligand Keskin, Seyma Goren; Stanley, Julie M.; Mitchell, Lauren A. Inorganica Chimica Acta, Vol. 486 https://doi.org/10.1016/j.ica.2018.10.030	journal	February 2019
1355. Hydrido-complexes of iridium(III) stabilised by tertiary phosphines and arsines Chatt, J.; Coffey, R. S.; Shaw, B. L. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9650007391	journal	January 1965
Synthesis of the New Chiral ( R )- and ( S )-Aminodiphosphine Ligands sec -Butylbis(2-(diphenylphosphino)ethyl)amine, sec -Butylbis(2-(dicyclohexylphosphino)ethyl)amine, and (α-Methylbenzyl)bis(2-(dicyclohexylphosphino)ethyl)amine and Their Organometallic Chemistry When Combined with Iridium Bianchini, Claudio; Glendenning, Lionel; Peruzzini, Maurizio Organometallics, Vol. 16, Issue 20 https://doi.org/10.1021/om9704455	journal	September 1997
Chemoselective Hydrogenation of Nitroarenes Using an Air-Stable Base-Metal Catalyst Zubar, Viktoriia; Dewanji, Abhishek; Rueping, Magnus Organic Letters, Vol. 23, Issue 7 https://doi.org/10.1021/acs.orglett.1c00659	journal	March 2021
CO ₂ Hydrogenation to Formate and Methanol as an Alternative to Photo- and Electrochemical CO ₂ Reduction Wang, Wan-Hui; Himeda, Yuichiro; Muckerman, James T. Chemical Reviews, Vol. 115, Issue 23 https://doi.org/10.1021/acs.chemrev.5b00197	journal	August 2015
Amination of Aliphatic Alcohols and Diols with an Iridium Pincer Catalyst Andrushko, Natalia; Andrushko, Vasyl; Roose, Peter ChemCatChem, Vol. 2, Issue 6 https://doi.org/10.1002/cctc.201000046	journal	June 2010
Selective Hydrogen Production from Methanol with a Defined Iron Pincer Catalyst under Mild Conditions Alberico, Elisabetta; Sponholz, Peter; Cordes, Christoph Angewandte Chemie International Edition, Vol. 52, Issue 52 https://doi.org/10.1002/anie.201307224	journal	December 2013
Formic Acid as a Hydrogen Energy Carrier Eppinger, Jörg; Huang, Kuo-Wei ACS Energy Letters, Vol. 2, Issue 1 https://doi.org/10.1021/acsenergylett.6b00574	journal	December 2016
Approaches to Sigma Complexes via Displacement of Agostic Interactions: An Experimental and Theoretical Investigation Ramaraj, A.; Reddy, K. Hari Krishna; Keil, Helena Organometallics, Vol. 36, Issue 15 https://doi.org/10.1021/acs.organomet.7b00210	journal	July 2017
Neutral Tridentate PNP Ligands and Their Hybrid Analogues: Versatile Non-Innocent Scaffolds for Homogeneous Catalysis van der Vlugt, Jarl Ivar; Reek, Joost N. H. Angewandte Chemie International Edition, Vol. 48, Issue 47 https://doi.org/10.1002/anie.200903193	journal	October 2009
Experimental Evidence of syn H–N–Fe–H Configurational Requirement for Iron-Based Bifunctional Hydrogenation Catalysts Dai, Huiguang; Li, Weishi; Krause, Jeanette A. Inorganic Chemistry, Vol. 60, Issue 9 https://doi.org/10.1021/acs.inorgchem.1c00328	journal	April 2021
Enhanced CO ₂ electroreduction efficiency through secondary coordination effects on a pincer iridium catalyst Ahn, Steven T.; Bielinski, Elizabeth A.; Lane, Elizabeth M. Chemical Communications, Vol. 51, Issue 27 https://doi.org/10.1039/C5CC00458F	journal	January 2015
Platinum complexes with a methoxy-amino phosphine or a nitrogen-containing bis(phosphine) ligand. Synthesis, characterization and application to hydrogenation of trans -cinnamaldehyde Kostas, Ioannis D.; Antonopoulou, Georgia; Potamitis, Constantinos Journal of Organometallic Chemistry, Vol. 828 https://doi.org/10.1016/j.jorganchem.2016.11.036	journal	January 2017
Dual Coordination Modes of Ethylene-Linked NP2 Ligands in Cobalt(II) and Nickel(II) Iodides Dong, Qingchen; Rose, Michael J.; Wong, Wai-Yeung Inorganic Chemistry, Vol. 50, Issue 20 https://doi.org/10.1021/ic201213c	journal	September 2011
Manganese-Catalyzed Sequential Hydrogenation of CO ₂ to Methanol via Formamide Kar, Sayan; Goeppert, Alain; Kothandaraman, Jotheeswari ACS Catalysis, Vol. 7, Issue 9 https://doi.org/10.1021/acscatal.7b02066	journal	August 2017
Iron catalyzed CO ₂ hydrogenation to formate enhanced by Lewis acid co-catalysts Zhang, Yuanyuan; MacIntosh, Alex D.; Wong, Janice L. Chemical Science, Vol. 6, Issue 7 https://doi.org/10.1039/C5SC01467K	journal	January 2015
Catalytic Formic Acid Dehydrogenation and CO ₂ Hydrogenation Using Iron PN ^R P Pincer Complexes with Isonitrile Ligands Curley, Julia B.; Smith, Nicholas E.; Bernskoetter, Wesley H. Organometallics, Vol. 37, Issue 21 https://doi.org/10.1021/acs.organomet.8b00534	journal	October 2018
A Molecular Iron Catalyst for the Acceptorless Dehydrogenation and Hydrogenation of N-Heterocycles Chakraborty, Sumit; Brennessel, William W.; Jones, William D. Journal of the American Chemical Society, Vol. 136, Issue 24 https://doi.org/10.1021/ja504523b	journal	June 2014
Catalytic Dehydrogenation of Formic Acid with Ruthenium‐PNP‐Pincer Complexes: Comparing N‐Methylated and NH‐Ligands Agapova, Anastasiya; Alberico, Elisabetta; Kammer, Anja ChemCatChem, Vol. 11, Issue 7 https://doi.org/10.1002/cctc.201801897	journal	March 2019
Influences of Bifunctional PNP-Pincer Ligands on Low Valent Cobalt Complexes Relevant to CO ₂ Hydrogenation Mills, Matthew R.; Barnes, Charles L.; Bernskoetter, Wesley H. Inorganic Chemistry, Vol. 57, Issue 3 https://doi.org/10.1021/acs.inorgchem.7b02931	journal	January 2018
Hydrogenation or Dehydrogenation of N-Containing Heterocycles Catalyzed by a Single Manganese Complex Zubar, Viktoriia; Borghs, Jannik C.; Rueping, Magnus Organic Letters, Vol. 22, Issue 10 https://doi.org/10.1021/acs.orglett.0c01273	journal	May 2020
Towards a Green Process for Bulk-Scale Synthesis of Ethyl Acetate: Efficient Acceptorless Dehydrogenation of Ethanol Nielsen, Martin; Junge, Henrik; Kammer, Anja Angewandte Chemie International Edition, Vol. 51, Issue 23 https://doi.org/10.1002/anie.201200625	journal	April 2012
Reversible Hydrogenation of Carbon Dioxide to Formic Acid and Methanol: Lewis Acid Enhancement of Base Metal Catalysts Bernskoetter, Wesley H.; Hazari, Nilay Accounts of Chemical Research, Vol. 50, Issue 4 https://doi.org/10.1021/acs.accounts.7b00039	journal	February 2017
Cobalt-Catalyzed Synthesis of Aromatic, Aliphatic, and Cyclic Secondary Amines via a “Hydrogen-Borrowing” Strategy Yin, Zhiwei; Zeng, Haisu; Wu, Jing ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b02218	journal	September 2016
Mild and Homogeneous Cobalt-Catalyzed Hydrogenation of CC, CO, and CN Bonds Zhang, Guoqi; Scott, Brian L.; Hanson, Susan K. Angewandte Chemie International Edition, Vol. 51, Issue 48 https://doi.org/10.1002/anie.201206051	journal	October 2012
Manganese Pincer Complexes for the Base-Free, Acceptorless Dehydrogenative Coupling of Alcohols to Esters: Development, Scope, and Understanding Nguyen, Duc Hanh; Trivelli, Xavier; Capet, Frédéric ACS Catalysis, Vol. 7, Issue 3 https://doi.org/10.1021/acscatal.6b03554	journal	February 2017
Amine-Free Reversible Hydrogen Storage in Formate Salts Catalyzed by Ruthenium Pincer Complex without pH Control or Solvent Change Kothandaraman, Jotheeswari; Czaun, Miklos; Goeppert, Alain ChemSusChem, Vol. 8, Issue 8 https://doi.org/10.1002/cssc.201403458	journal	March 2015
Enabling storage and utilization of low-carbon electricity: power to formic acid Chatterjee, Sudipta; Dutta, Indranil; Lum, Yanwei Energy & Environmental Science, Vol. 14, Issue 3 https://doi.org/10.1039/D0EE03011B	journal	January 2021
Understanding the Reactivity and Decomposition of a Highly Active Iron Pincer Catalyst for Hydrogenation and Dehydrogenation Reactions Curley, Julia B.; Smith, Nicholas E.; Bernskoetter, Wesley H. ACS Catalysis, Vol. 11, Issue 16 https://doi.org/10.1021/acscatal.1c03347	journal	August 2021
Key factors in pincer ligand design Peris, Eduardo; Crabtree, Robert H. Chemical Society Reviews, Vol. 47, Issue 6 https://doi.org/10.1039/C7CS00693D	journal	January 2018
Iron-Based Catalysts for the Hydrogenation of Esters to Alcohols Chakraborty, Sumit; Dai, Huiguang; Bhattacharya, Papri Journal of the American Chemical Society, Vol. 136, Issue 22 https://doi.org/10.1021/ja504034q	journal	May 2014

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Organic acids
Ligands
Organic reactions
Catalysts
Molecular structure

CCDC 2109547: Experimental Crystal Structure Determination B., Curley, Julia; Clayton, Hert,; H., Bernskoetter, Wesley https://doi.org/10.5517/ccdc.csd.cc28t4x5 The current record is supplemented by this dataset	dataset	January 2021
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Title: Control of Catalyst Isomers Using an N-Phenyl-Substituted RN(CH₂CH₂PⁱPr₂)₂ Pincer Ligand in CO₂ Hydrogenation and Formic Acid Dehydrogenation