C–H Bond Activation Facilitated by Bis(phosphinoamide) Heterobimetallic Zr/Co Complexes

Hunter, Nathanael H.; Lane, Elizabeth M.; Gramigna, Kathryn M.; Moore, Curtis E.; Thomas, Christine M.

doi:10.1021/acs.organomet.1c00511

Title: C–H Bond Activation Facilitated by Bis(phosphinoamide) Heterobimetallic Zr/Co Complexes

Journal Article · Wed Oct 20 00:00:00 EDT 2021 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.1c00511· OSTI ID:1835591

Hunter, Nathanael H. ^[1]; Lane, Elizabeth M. ^[1]; Gramigna, Kathryn M. ^[2];

^[1];

^[1]

The Ohio State Univ., Columbus, OH (United States)
Brandeis Univ., Waltham, MA (United States)

The activation of C–H bonds using first-row transition metals poses a formidable challenge in the development of sustainable catalytic methods. Early/late heterobimetallic complexes provide a Lewis acidic binding site for directing groups, facilitating the activation of C–H bonds at an appended first-row transition metal center. In this work, the reactivity of the ZrIV/Co–I heterobimetallic complexes (THF)(I)Zr(XylNPⁱPr₂)₂Co(PR₃) (1-PR₃; Xyl = 3,5-dimethylphenyl; PR₃ = PMe₃, PPh₂Me) toward directed C–H bond activation is explored with pyridine and terminal alkyne derivatives. 1-PMe₃ reacts reversibly with 4-methylpyridine to afford the C–H activated complex (4-Me-C₅H₄N)(I)Zr(XylNPⁱPr₂)₂(μ-4-Me-C₅H₃N)Co(PMe₃)(H) (3-PMe₃). By using the more Lewis basic substrate 4-tert-butylpyridine, (I)Zr(XylNPⁱPr₂)2(μ-4-^tBu-C₅H₃N)Co(PMe₃)(H) (4-PMe₃) is formed irreversibly. In addition to pyridine derivatives, 1-PPh₂Me can activate the C–H bond of terminal alkynes to form (THF)(I)Zr(XylNPiPr₂)₂(μ-R'C≡C)Co(PPh₂Me)(H) (R' = Ph (5-PPh₂Me); R' = SiMe₃ (6-PPh₂Me)).

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019179

OSTI ID:: 1835591

Journal Information:: Organometallics, Vol. 40, Issue 21; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (59)

Introduction: CH Activation Crabtree, Robert H.; Lei, Aiwen Chemical Reviews, Vol. 117, Issue 13 https://doi.org/10.1021/acs.chemrev.7b00307	journal	March 2017
C–H activation Bergman, Robert G. Nature, Vol. 446, Issue 7134 https://doi.org/10.1038/446391a	journal	March 2007
C(sp ² )–H Activation with Pyridine Dicarbene Iron Dialkyl Complexes: Hydrogen Isotope Exchange of Arenes Using Benzene- d ₆ as a Deuterium Source Corpas, Javier; Viereck, Peter; Chirik, Paul J. ACS Catalysis, Vol. 10, Issue 15 https://doi.org/10.1021/acscatal.0c01714	journal	July 2020
Iron-Catalyzed C–H Bond Activation Shang, Rui; Ilies, Laurean; Nakamura, Eiichi Chemical Reviews, Vol. 117, Issue 13 https://doi.org/10.1021/acs.chemrev.6b00772	journal	March 2017
Structure and Reactivity of Early−Late Heterobimetallic Complexes ^† Wheatley, Nigel; Kalck, Philippe Chemical Reviews, Vol. 99, Issue 12 https://doi.org/10.1021/cr980325m	journal	December 1999
Cobalt-Catalyzed C–H Borylation Obligacion, Jennifer V.; Semproni, Scott P.; Chirik, Paul J. Journal of the American Chemical Society, Vol. 136, Issue 11 https://doi.org/10.1021/ja500712z	journal	March 2014
Cooperative H ₂ Activation across a Metal–Metal Multiple Bond and Hydrogenation Reactions Catalyzed by a Zr/Co Heterobimetallic Complex Gramigna, Kathryn M.; Dickie, Diane A.; Foxman, Bruce M. ACS Catalysis, Vol. 9, Issue 4 https://doi.org/10.1021/acscatal.8b04390	journal	March 2019
Early-late heterobimetallics Stephan, Douglas W. Coordination Chemistry Reviews, Vol. 95, Issue 1 https://doi.org/10.1016/0010-8545(89)80002-5	journal	June 1989
Mechanistic Studies of Cobalt-Catalyzed C(sp ² )–H Borylation of Five-Membered Heteroarenes with Pinacolborane Obligacion, Jennifer V.; Chirik, Paul J. ACS Catalysis, Vol. 7, Issue 7 https://doi.org/10.1021/acscatal.7b01151	journal	May 2017
A Cp*CoI ₂ -dimer as a precursor for cationic Co( iii )-catalysis: application to C–H phosphoramidation of indoles Sun, Bo; Yoshino, Tatsuhiko; Matsunaga, Shigeki Chemical Communications, Vol. 51, Issue 22 https://doi.org/10.1039/C4CC10284C	journal	January 2015
A Catalytic Application of Co/Zr Heterobimetallic Complexes: Kumada Coupling of Unactivated Alkyl Halides with Alkyl Grignard Reagents Zhou, Wen; Napoline, Jonathan Wesley; Thomas, Christine M. European Journal of Inorganic Chemistry, Vol. 2011, Issue 13 https://doi.org/10.1002/ejic.201100109	journal	March 2011
Isotope Effects in C−H Bond Activation Reactions by Transition Metals Jones, William D. Accounts of Chemical Research, Vol. 36, Issue 2 https://doi.org/10.1021/ar020148i	journal	February 2003
Reaction of sp2 carbon-hydrogen bonds in unactivated alkenes with bis(diphosphine) complexes of iron Baker, Murray V.; Field, Leslie D. Journal of the American Chemical Society, Vol. 108, Issue 23 https://doi.org/10.1021/ja00283a062	journal	November 1986
Dimerization of terminal alkynes promoted by a heterobimetallic Zr/Co complex Beattie, Jeffrey W.; Wang, Canning; Zhang, Hongtu Dalton Transactions, Vol. 49, Issue 8 https://doi.org/10.1039/D0DT00334D	journal	January 2020
Rhodium‐Catalyzed C−H Activation Enabled by an Indium Metalloligand Yamada, Ryosuke; Iwasawa, Nobuharu; Takaya, Jun Angewandte Chemie International Edition, Vol. 58, Issue 48 https://doi.org/10.1002/anie.201910197	journal	November 2019
Iron-Catalyzed Chemoselective ortho Arylation of Aryl Imines by Directed CH Bond Activation Yoshikai, Naohiko; Matsumoto, Arimasa; Norinder, Jakob Angewandte Chemie International Edition, Vol. 48, Issue 16 https://doi.org/10.1002/anie.200900454	journal	March 2009
Catalytic Functionalization of Arenes and Alkanes via C−H Bond Activation Jia, Chengguo; Kitamura, Tsugio; Fujiwara, Yuzo Accounts of Chemical Research, Vol. 34, Issue 8 https://doi.org/10.1021/ar000209h	journal	May 2001
Activation of CO ₂ by a Heterobimetallic Zr/Co Complex Krogman, Jeremy P.; Foxman, Bruce M.; Thomas, Christine M. Journal of the American Chemical Society, Vol. 133, Issue 37 https://doi.org/10.1021/ja2071847	journal	September 2011
Weak Coordination as a Powerful Means for Developing Broadly Useful C–H Functionalization Reactions Engle, Keary M.; Mei, Tian-Sheng; Wasa, Masayuki Accounts of Chemical Research, Vol. 45, Issue 6 https://doi.org/10.1021/ar200185g	journal	December 2011
Cobalt-Catalyzed C–H Activation Moselage, Marc; Li, Jie; Ackermann, Lutz ACS Catalysis, Vol. 6, Issue 2 https://doi.org/10.1021/acscatal.5b02344	journal	December 2015
Enabling Two-Electron Pathways with Iron and Cobalt: From Ligand Design to Catalytic Applications Arevalo, Rebeca; Chirik, Paul J. Journal of the American Chemical Society, Vol. 141, Issue 23 https://doi.org/10.1021/jacs.9b03337	journal	May 2019
meta-Selective C–H Borylation of Benzamides and Pyridines by an Iridium–Lewis Acid Bifunctional Catalyst Yang, Lichen; Uemura, Nao; Nakao, Yoshiaki Journal of the American Chemical Society, Vol. 141, Issue 19 https://doi.org/10.1021/jacs.9b03138	journal	April 2019
Iron-Catalyzed C–H Borylation of Arenes Dombray, Thomas; Werncke, C. Gunnar; Jiang, Shi Journal of the American Chemical Society, Vol. 137, Issue 12 https://doi.org/10.1021/jacs.5b00895	journal	March 2015
Mechanistic Interrogation of Alkyne Hydroarylations Catalyzed by Highly Reduced, Single-Component Cobalt Complexes Suslick, Benjamin A.; Tilley, T. Don Journal of the American Chemical Society, Vol. 142, Issue 25 https://doi.org/10.1021/jacs.0c04072	journal	May 2020
Synthesis and Reactivity of Early−Late Heterobimetallic Hydrides of Group 4 Metals and Iridium Supported by Mono(η ⁵ -C ₅ Me ₅ ) Ancillary Ligands: Bimetallic Carbon−Hydrogen Bond Activation Oishi, Masataka; Kato, Takeshi; Nakagawa, Mayuko Organometallics, Vol. 27, Issue 23 https://doi.org/10.1021/om800715b	journal	November 2008
C–H Functionalization in organic synthesis Davies, Huw M. L.; Du Bois, Justin; Yu, Jin-Quan Chemical Society Reviews, Vol. 40, Issue 4 https://doi.org/10.1039/c1cs90010b	journal	January 2011
A heterobimetallic complex featuring a Ti–Co multiple bond and its application to the reductive coupling of ketones to alkenes Wu, Bing; Bezpalko, Mark W.; Foxman, Bruce M. Chemical Science, Vol. 6, Issue 3 https://doi.org/10.1039/C4SC03772C	journal	January 2015
Transient and matrix photochemistry of Fe(dmpe)2H2 (dmpe = Me2PCH2CH2Me2): dynamics of C-H and H-H activation Whittlesey, Michael K.; Mawby, Roger J.; Osman, Robert Journal of the American Chemical Society, Vol. 115, Issue 19 https://doi.org/10.1021/ja00072a016	journal	September 1993
Why Two Metals Are Better Than One for Heterodinuclear Cobalt–Zirconium-Catalyzed Kumada Coupling Coombs, Jimmy; Perry, Dalton; Kwon, Doo-Hyun Organometallics, Vol. 37, Issue 22 https://doi.org/10.1021/acs.organomet.8b00449	journal	November 2018
Effect of ligand modification on the reactivity of phosphinoamide-bridged heterobimetallic Zr/Co complexes Zhou, Wen; Saper, Noam I.; Krogman, Jeremy P. Dalton Trans., Vol. 43, Issue 5 https://doi.org/10.1039/C3DT52133H	journal	January 2014
Chemistry of 2-naphthyl bis[bis(dimethylphosphino)ethane] hydride complexes of iron, ruthenium, and osmium. 3. Cleavage of sp2 carbon-hydrogen bonds Tolman, C. A.; Ittel, S. D.; English, A. D. Journal of the American Chemical Society, Vol. 101, Issue 7 https://doi.org/10.1021/ja00501a017	journal	March 1979
A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry Sambiagio, Carlo; Schönbauer, David; Blieck, Remi Chemical Society Reviews, Vol. 47, Issue 17 https://doi.org/10.1039/C8CS00201K	journal	January 2018
Selective ortho C–H Activation of Pyridines Directed by Lewis Acidic Boron of PBP Pincer Iridium Complexes Shih, Wei-Chun; Ozerov, Oleg V. Journal of the American Chemical Society, Vol. 139, Issue 48 https://doi.org/10.1021/jacs.7b10570	journal	November 2017
Catalytic Applications of Early/Late Heterobimetallic Complexes Cooper, Benjamin G.; Napoline, J. Wesley; Thomas, Christine M. Catalysis Reviews, Vol. 54, Issue 1 https://doi.org/10.1080/01614940.2012.619931	journal	January 2012
Heterobimetallic .sigma.,.pi.-Acetylide-Bridged Complexes from Disubstituted 1,3-Butadiynes Rosenthal, Uwe; Pulst, Siegmar; Arndt, Perdita Organometallics, Vol. 14, Issue 6 https://doi.org/10.1021/om00006a046	journal	June 1995
Experimental Evidence for a Temperature Dependent Transition between Normal and Inverse Equilibrium Isotope Effects for Oxidative Addition of H ₂ to Ir(PMe ₂ Ph) ₂ (CO)Cl Janak, Kevin E.; Parkin, Gerard Journal of the American Chemical Society, Vol. 125, Issue 43 https://doi.org/10.1021/ja0362611	journal	October 2003
Low-Valent Cobalt Catalysis: New Opportunities for C–H Functionalization Gao, Ke; Yoshikai, Naohiko Accounts of Chemical Research, Vol. 47, Issue 4 https://doi.org/10.1021/ar400270x	journal	February 2014
3d Transition Metals for C–H Activation Gandeepan, Parthasarathy; Müller, Thomas; Zell, Daniel Chemical Reviews, Vol. 119, Issue 4 https://doi.org/10.1021/acs.chemrev.8b00507	journal	October 2018
Metal-Metal Multiple Bonds in Early/Late Heterobimetallic Complexes: Applications Toward Small Molecule Activation and Catalysis Thomas, Christine M. Comments on Inorganic Chemistry, Vol. 32, Issue 1 https://doi.org/10.1080/02603594.2011.593213	journal	January 2011
Exploration of Earth-Abundant Transition Metals (Fe, Co, and Ni) as Catalysts in Unreactive Chemical Bond Activations Su, Bo; Cao, Zhi-Chao; Shi, Zhang-Jie Accounts of Chemical Research, Vol. 48, Issue 3 https://doi.org/10.1021/ar500345f	journal	February 2015
Multimetallic Catalysis Based on Heterometallic Complexes and Clusters Buchwalter, Paulin; Rosé, Jacky; Braunstein, Pierre Chemical Reviews, Vol. 115, Issue 1 https://doi.org/10.1021/cr500208k	journal	November 2014
Investigation of Ketone C═O Bond Activation Processes by Heterobimetallic Zr/Co and Ti/Co Tris(phosphinoamide) Complexes Zhang, Hongtu; Wu, Bing; Marquard, Seth L. Organometallics, Vol. 36, Issue 18 https://doi.org/10.1021/acs.organomet.7b00445	journal	September 2017
Recent Advances in C–H Functionalization Davies, Huw M. L.; Morton, Daniel The Journal of Organic Chemistry, Vol. 81, Issue 2 https://doi.org/10.1021/acs.joc.5b02818	journal	January 2016
Metal–metal multiple bonding in C3-symmetric bimetallic complexes of the first row transition metals Krogman, Jeremy P.; Thomas, Christine M. Chemical Communications, Vol. 50, Issue 40 https://doi.org/10.1039/c3cc47537a	journal	January 2014
Cooperative Bond Activation and Facile Intramolecular Aryl Transfer of Nickel–Aluminum Pincer‐type Complexes Graziano, Brendan J.; Vollmer, Matthew V.; Lu, Connie C. Angewandte Chemie International Edition, Vol. 60, Issue 27 https://doi.org/10.1002/anie.202104050	journal	June 2021
C(sp ² )–H Borylation of Heterocycles by Well-Defined Bis(silylene)pyridine Cobalt(III) Precatalysts: Pincer Modification, C(sp ² )–H Activation, and Catalytically Relevant Intermediates Arevalo, Rebeca; Pabst, Tyler P.; Chirik, Paul J. Organometallics, Vol. 39, Issue 14 https://doi.org/10.1021/acs.organomet.0c00382	journal	July 2020
Rhodium Catalyzed Chelation-Assisted C–H Bond Functionalization Reactions Colby, Denise A.; Tsai, Andy S.; Bergman, Robert G. Accounts of Chemical Research, Vol. 45, Issue 6 https://doi.org/10.1021/ar200190g	journal	December 2011
Stoichiometric C═O Bond Oxidative Addition of Benzophenone by a Discrete Radical Intermediate To Form a Cobalt(I) Carbene Marquard, Seth L.; Bezpalko, Mark W.; Foxman, Bruce M. Journal of the American Chemical Society, Vol. 135, Issue 16 https://doi.org/10.1021/ja4022683	journal	April 2013
Platinum-Catalyzed C–H Functionalization Labinger, Jay A. Chemical Reviews, Vol. 117, Issue 13 https://doi.org/10.1021/acs.chemrev.6b00583	journal	October 2016
Heterobimetallic compounds linked by heterodifunctional ligands Bullock, R. Morris; Casey, Charles P. Accounts of Chemical Research, Vol. 20, Issue 5 https://doi.org/10.1021/ar00137a002	journal	May 1987
Carbon-hydrogen activation in completely saturated hydrocarbons: direct observation of M + R-H .fwdarw. M(R)(H) Janowicz, Andrew H.; Bergman, Robert G. Journal of the American Chemical Society, Vol. 104, Issue 1 https://doi.org/10.1021/ja00365a091	journal	January 1982
C–H Activation: Toward Sustainability and Applications Dalton, Toryn; Faber, Teresa; Glorius, Frank ACS Central Science, Vol. 7, Issue 2 https://doi.org/10.1021/acscentsci.0c01413	journal	February 2021
Transition metal-catalyzed C–H bond functionalizations by the use of diverse directing groups Chen, Zhengkai; Wang, Binjie; Zhang, Jitan Organic Chemistry Frontiers, Vol. 2, Issue 9 https://doi.org/10.1039/C5QO00004A	journal	January 2015
Rhodium Complexes Bearing PAlP Pincer Ligands Hara, Naofumi; Saito, Teruhiko; Semba, Kazuhiko Journal of the American Chemical Society, Vol. 140, Issue 23 https://doi.org/10.1021/jacs.8b04199	journal	May 2018
On the Interpretation of Deuterium Kinetic Isotope Effects in CH Bond Functionalizations by Transition-Metal Complexes Simmons, Eric M.; Hartwig, John F. Angewandte Chemie International Edition, Vol. 51, Issue 13 https://doi.org/10.1002/anie.201107334	journal	March 2012
Metal−Metal Multiple Bonds in Early/Late Heterobimetallics Support Unusual Trigonal Monopyramidal Geometries at both Zr and Co Greenwood, Bennett P.; Rowe, Gerard T.; Chen, Chun-Hsing Journal of the American Chemical Society, Vol. 132, Issue 1 https://doi.org/10.1021/ja909310t	journal	January 2010
Reaction of carbon-hydrogen bonds in alkanes with bis(diphosphine) complexes of iron Baker, Murray V.; Field, Leslie D. Journal of the American Chemical Society, Vol. 109, Issue 9 https://doi.org/10.1021/ja00243a046	journal	April 1987
Evolution of C–H Bond Functionalization from Methane to Methodology Hartwig, John F. Journal of the American Chemical Society, Vol. 138, Issue 1 https://doi.org/10.1021/jacs.5b08707	journal	December 2015
Homogeneous metal-catalyzed exchange of aromatic compounds. Isotopic hydrogen labeling procedure Garnett, John L.; Hodges, R. J. Journal of the American Chemical Society, Vol. 89, Issue 17 https://doi.org/10.1021/ja00993a067	journal	August 1967

Linked Research (2)

Similar Records

Use of the electron-reservoir [Fe{sup I}Cp(arene)] sandwiches as efficient and selective electrocatalysts: Syntheses of homo- and heterodinuclear zwitterionic transition-metal fulvalene complexes

Journal Article · Tue Apr 30 00:00:00 EDT 1996 · Organometallics · OSTI ID:1835591

Brown, D S; Vollhardt, K P.C.; Delville, M H; +1 more

Synthesis and Reactivity of Palladium(II) Alkyl Complexes that Contain Phosphine-cyclopentanesulfonate Ligands

Journal Article · Wed Aug 23 00:00:00 EDT 2017 · Organometallics · OSTI ID:1835591

Black, Rebecca E.; Jordan, Richard F.

Carbene complexes of zirconium. Synthesis, structure, and reactivity with carbon monoxide to affort coordinated ketene

Journal Article · Wed Sep 05 00:00:00 EDT 1984 · J. Am. Chem. Soc.; (United States) · OSTI ID:1835591

Barger, P T; Santarsiero, B D; Armantrout, J; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Hydrocarbons
Ligands
Pyridines
Transition metals
Nuclear magnetic resonance spectroscopy

CCDC 2096329: Experimental Crystal Structure Determination H., Hunter, Nathanael; M., Lane, Elizabeth; M., Gramigna, Kathryn https://doi.org/10.5517/ccdc.csd.cc28cdjl The current record is supplemented by this dataset	dataset	January 2021
CCDC 2096330: Experimental Crystal Structure Determination H., Hunter, Nathanael; M., Lane, Elizabeth; M., Gramigna, Kathryn https://doi.org/10.5517/ccdc.csd.cc28cdkm The current record is supplemented by this dataset	dataset	January 2021

Title: C–H Bond Activation Facilitated by Bis(phosphinoamide) Heterobimetallic Zr/Co Complexes

Citation Formats

References (59)

Linked Research (2)

Similar Records

Related Subjects