Synthesis, Electronic Structure, and Reactivity of a Planar Four‐Coordinate, Cobalt–Imido Complex

Park, Yoonsu; Semproni, Scott P.; Zhong, Hongyu; Chirik, Paul J.

doi:10.1002/ange.202104320

Synthesis, Electronic Structure, and Reactivity of a Planar Four‐Coordinate, Cobalt–Imido Complex

Journal Article · Mon May 24 00:00:00 EDT 2021 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202104320· OSTI ID:1784570

^[1]; Semproni, Scott P. ^[1]; Zhong, Hongyu ^[1]; ^[1]

Department of Chemistry Princeton University Frick Laboratory 292 Princeton NJ 08544 USA

Abstract

A four‐coordinate cobalt–imido complex, ( ^{t Bu} mPNP)Co=NMes ( ^{t Bu} mPNP=modified PNP pincer ligand) has been synthesized from addition of 2,4,6‐trimethylphenylazide (Mes–N ₃ ) to the corresponding dinitrogen complex. The solid‐state structure determined by X‐ray diffraction established a rare, idealized planar geometry with a Co=N bond distance of 1.716(2) Å. Magnetic measurements revealed an S =1 ground state with CAS‐SCF calculations supporting radical character on the imide nitrogen. Thermolysis of the cobalt–imido compound induced selective insertion of the imido group into a Co−P bond and yielded a three‐coordinate cobalt complex with a distorted T‐shaped geometry. Transition state analysis conducted with DFT calculations established the thermodynamic stability of the P–N coupled product and provided insight into the exclusive selectivity.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; SC0006498

OSTI ID:: 1784570

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 26 Vol. 133; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (67)

Intramolecular C?H Activation by an Open-Shell Cobalt(III) Imido Complex Shay, Daniel T.; Yap, Glenn P. A.; Zakharov, Lev N. Angewandte Chemie, Vol. 117, Issue 10 https://doi.org/10.1002/ange.200462529	journal	February 2005
Coordination-Number Dependence of Reactivity in an Imidoiron(III) Complex Eckert, Nathan A.; Vaddadi, Sridhar; Stoian, Sebastian Angewandte Chemie, Vol. 118, Issue 41 https://doi.org/10.1002/ange.200601927	journal	October 2006
Amidinato- and Guanidinato-Cobalt(I) Complexes: Characterization of Exceptionally Short Co-Co Interactions Jones, Cameron; Schulten, Christian; Rose, Richard P. Angewandte Chemie, Vol. 121, Issue 40 https://doi.org/10.1002/ange.200900780	journal	September 2009
A Two-Coordinate Cobalt(II) Imido Complex with NHC Ligation: Synthesis, Structure, and Reactivity Du, Jingzhen; Wang, Linbo; Xie, Meihua Angewandte Chemie, Vol. 127, Issue 43 https://doi.org/10.1002/ange.201505937	journal	August 2015
Ring-Size-Modulated Reactivity of Putative Dicobalt-Bridging Nitrides: C−H Activation versus Phosphinimide Formation Cui, Peng; Wang, Qiuran; McCollom, Samuel P. Angewandte Chemie, Vol. 129, Issue 50 https://doi.org/10.1002/ange.201708966	journal	November 2017
A Low‐Spin Three‐Coordinate Cobalt(I) Complex and Its Reactivity toward H ₂ and Silane Choi, Jonghoon; Lee, Yunho Angewandte Chemie, Vol. 131, Issue 21 https://doi.org/10.1002/ange.201901007	journal	April 2019
C‐H‐Bindungsaktivierung durch einen Imidocobalt(III)‐ und den resultierenden Amidocobalt(II)‐Komplex Reckziegel, Alexander; Pietzonka, Clemens; Kraus, Florian Angewandte Chemie, Vol. 132, Issue 22 https://doi.org/10.1002/ange.201914718	journal	March 2020
Intramolecular C?H Activation by an Open-Shell Cobalt(III) Imido Complex Shay, Daniel T.; Yap, Glenn P. A.; Zakharov, Lev N. Angewandte Chemie International Edition, Vol. 44, Issue 10 https://doi.org/10.1002/anie.200462529	journal	February 2005
Coordination-Number Dependence of Reactivity in an Imidoiron(III) Complex Eckert, Nathan A.; Vaddadi, Sridhar; Stoian, Sebastian Angewandte Chemie International Edition, Vol. 45, Issue 41 https://doi.org/10.1002/anie.200601927	journal	October 2006
Amidinato- and Guanidinato-Cobalt(I) Complexes: Characterization of Exceptionally Short Co-Co Interactions Jones, Cameron; Schulten, Christian; Rose, Richard P. Angewandte Chemie International Edition, Vol. 48, Issue 40 https://doi.org/10.1002/anie.200900780	journal	September 2009
A Two-Coordinate Cobalt(II) Imido Complex with NHC Ligation: Synthesis, Structure, and Reactivity Du, Jingzhen; Wang, Linbo; Xie, Meihua Angewandte Chemie International Edition, Vol. 54, Issue 43 https://doi.org/10.1002/anie.201505937	journal	August 2015
Ring-Size-Modulated Reactivity of Putative Dicobalt-Bridging Nitrides: C−H Activation versus Phosphinimide Formation Cui, Peng; Wang, Qiuran; McCollom, Samuel P. Angewandte Chemie International Edition, Vol. 56, Issue 50 https://doi.org/10.1002/anie.201708966	journal	November 2017
A Low‐Spin Three‐Coordinate Cobalt(I) Complex and Its Reactivity toward H ₂ and Silane Choi, Jonghoon; Lee, Yunho Angewandte Chemie International Edition, Vol. 58, Issue 21 https://doi.org/10.1002/anie.201901007	journal	May 2019
C−H Bond Activation by an Imido Cobalt(III) and the Resulting Amido Cobalt(II) Complex Reckziegel, Alexander; Pietzonka, Clemens; Kraus, Florian Angewandte Chemie International Edition, Vol. 59, Issue 22 https://doi.org/10.1002/anie.201914718	journal	March 2020
Cobalt–Pincer Complexes in Catalysis Junge, Kathrin; Papa, Veronica; Beller, Matthias Chemistry – A European Journal, Vol. 25, Issue 1 https://doi.org/10.1002/chem.201803016	journal	December 2018
ME and ME complexes of iron and cobalt that emphasize three-fold symmetry (E=O, N, NR) Saouma, Caroline T.; Peters, Jonas C. Coordination Chemistry Reviews, Vol. 255, Issue 7-8 https://doi.org/10.1016/j.ccr.2011.01.009	journal	April 2011
Iron- and Cobalt-Catalyzed Alkene Hydrogenation: Catalysis with Both Redox-Active and Strong Field Ligands Chirik, Paul J. Accounts of Chemical Research, Vol. 48, Issue 6 https://doi.org/10.1021/acs.accounts.5b00134	journal	May 2015
Tunable, Chemo- and Site-Selective Nitrene Transfer Reactions through the Rational Design of Silver(I) Catalysts Alderson, Juliet M.; Corbin, Joshua R.; Schomaker, Jennifer M. Accounts of Chemical Research, Vol. 50, Issue 9 https://doi.org/10.1021/acs.accounts.7b00178	journal	August 2017
Transition Metal-Catalyzed C–H Amination: Scope, Mechanism, and Applications Park, Yoonsu; Kim, Youyoung; Chang, Sukbok Chemical Reviews, Vol. 117, Issue 13 https://doi.org/10.1021/acs.chemrev.6b00644	journal	January 2017
An Unusual Cobalt Azide Adduct That Produces a Nitrene Species for Carbon–Hydrogen Insertion Chemistry Grant, Lauren N.; Carroll, Maria E.; Carroll, Patrick J. Inorganic Chemistry, Vol. 55, Issue 16 https://doi.org/10.1021/acs.inorgchem.6b01114	journal	July 2016
Square Planar Cobalt(II) Hydride versus T-Shaped Cobalt(I): Structural Characterization and Dihydrogen Activation with PNP–Cobalt Pincer Complexes Merz, Lukas S.; Blasius, Clemens K.; Wadepohl, Hubert Inorganic Chemistry, Vol. 58, Issue 9 https://doi.org/10.1021/acs.inorgchem.9b00384	journal	April 2019
Facile Activation and Deoxygenative Metathesis of CO MacNeil, Connor S.; Glynn, Kayla E.; Hayes, Paul G. Organometallics, Vol. 37, Issue 19 https://doi.org/10.1021/acs.organomet.8b00652	journal	September 2018
Dioxazolones: Stable Substrates for the Catalytic Transfer of Acyl Nitrenes van Vliet, Kaj M.; de Bruin, Bas ACS Catalysis, Vol. 10, Issue 8 https://doi.org/10.1021/acscatal.0c00961	journal	March 2020
Cobalt Pincer Complexes in Catalytic C–H Borylation: The Pincer Ligand Flips Rather Than Dearomatizes Li, Haixia; Obligacion, Jennifer V.; Chirik, Paul J. ACS Catalysis, Vol. 8, Issue 11 https://doi.org/10.1021/acscatal.8b03146	journal	September 2018
Metal-Catalyzed Nitrogen-Atom Transfer Methods for the Oxidation of Aliphatic C–H Bonds Roizen, Jennifer L.; Harvey, Mark Edwin; Du Bois, J. Accounts of Chemical Research, Vol. 45, Issue 6 https://doi.org/10.1021/ar200318q	journal	January 2012
Exploring the Reactivity of Four-Coordinate PNPCoX with Access to Three-Coordinate Spin Triplet PNPCo Ingleson, Michael J.; Pink, Maren; Fan, Hongjun Inorganic Chemistry, Vol. 46, Issue 24 https://doi.org/10.1021/ic701171p	journal	November 2007
Bonding and Structure of Copper Nitrenes Cundari, Thomas R.; Dinescu, Adriana; Kazi, Abul B. Inorganic Chemistry, Vol. 47, Issue 21 https://doi.org/10.1021/ic801337f	journal	November 2008
Monomeric (pentamethylcyclopentadienyl)iridium imido compounds: synthesis, structure, and reactivity Glueck, David S.; Wu, Jianxin; Hollander, Frederick J. Journal of the American Chemical Society, Vol. 113, Issue 6 https://doi.org/10.1021/ja00006a026	journal	March 1991
Terminal Amido and Imido Complexes of Three-Coordinate Nickel Mindiola, Daniel J.; Hillhouse, Gregory L. Journal of the American Chemical Society, Vol. 123, Issue 19 https://doi.org/10.1021/ja010358a	journal	May 2001
Oxidative Group Transfer to Co(I) Affords a Terminal Co(III) Imido Complex Jenkins, David M.; Betley, Theodore A.; Peters, Jonas C. Journal of the American Chemical Society, Vol. 124, Issue 38 https://doi.org/10.1021/ja026852b	journal	September 2002
A Low-Spin d ⁵ Iron Imide: Nitrene Capture by Low-Coordinate Iron(I) Provides the 4-Coordinate Fe(III) Complex [PhB(CH ₂ PPh ₂ ) ₃ ]Fe⋮N- p -tolyl Brown, Steven D.; Betley, Theodore A.; Peters, Jonas C. Journal of the American Chemical Society, Vol. 125, Issue 2 https://doi.org/10.1021/ja028448i	journal	January 2003
[Me ₂ NN]Co(η ⁶ -toluene): OO, NN, and ON Bond Cleavage Provides β-Diketiminato Cobalt μ-Oxo and Imido Complexes Dai, Xuliang; Kapoor, Pooja; Warren, Timothy H. Journal of the American Chemical Society, Vol. 126, Issue 15 https://doi.org/10.1021/ja036308i	journal	April 2004
Terminal Cobalt(III) Imido Complexes Supported by Tris(Carbene) Ligands: Imido Insertion into the Cobalt−Carbene Bond Hu, Xile; Meyer, Karsten Journal of the American Chemical Society, Vol. 126, Issue 50 https://doi.org/10.1021/ja044271b	journal	December 2004
Synthesis and Hydrogenation of Bis(imino)pyridine Iron Imides Bart, Suzanne C.; Lobkovsky, Emil; Bill, Eckhard Journal of the American Chemical Society, Vol. 128, Issue 16 https://doi.org/10.1021/ja057165y	journal	April 2006
Formation of a Cobalt(III) Imido from a Cobalt(II) Amido Complex. Evidence for Proton-Coupled Electron Transfer Cowley, Ryan E.; Bontchev, Ranko P.; Sorrell, John Journal of the American Chemical Society, Vol. 129, Issue 9 https://doi.org/10.1021/ja066899n	journal	March 2007
Photolysis and Thermolysis of Bis(imino)pyridine Cobalt Azides: C−H Activation from Putative Cobalt Nitrido Complexes Hojilla Atienza, Crisita Carmen; Bowman, Amanda C.; Lobkovsky, Emil Journal of the American Chemical Society, Vol. 132, Issue 46 https://doi.org/10.1021/ja107288x	journal	November 2010
Selectivity and Mechanism of Hydrogen Atom Transfer by an Isolable Imidoiron(III) Complex Cowley, Ryan E.; Eckert, Nathan A.; Vaddadi, Sridhar Journal of the American Chemical Society, Vol. 133, Issue 25 https://doi.org/10.1021/ja2005303	journal	June 2011
Mechanism of Cobalt(II) Porphyrin-Catalyzed C–H Amination with Organic Azides: Radical Nature and H-Atom Abstraction Ability of the Key Cobalt(III)–Nitrene Intermediates Lyaskovskyy, Volodymyr; Suarez, Alma I. Olivos; Lu, Hongjian Journal of the American Chemical Society, Vol. 133, Issue 31 https://doi.org/10.1021/ja204800a	journal	August 2011
Co(III) Imidos Exhibiting Spin Crossover and C–H Bond Activation King, Evan R.; Sazama, Graham T.; Betley, Theodore A. Journal of the American Chemical Society, Vol. 134, Issue 43 https://doi.org/10.1021/ja307699u	journal	October 2012
Four-Coordinate Cobalt Pincer Complexes: Electronic Structure Studies and Ligand Modification by Homolytic and Heterolytic Pathways Semproni, Scott P.; Milsmann, Carsten; Chirik, Paul J. Journal of the American Chemical Society, Vol. 136, Issue 25 https://doi.org/10.1021/ja504334a	journal	June 2014
An Intermediate Cobalt(IV) Nitrido Complex and its N-Migratory Insertion Product Zolnhofer, Eva M.; Käß, Martina; Khusniyarov, Marat M. Journal of the American Chemical Society, Vol. 136, Issue 42 https://doi.org/10.1021/ja508144j	journal	October 2014
Three-Coordinate Cobalt(IV) and Cobalt(V) Imido Complexes with N-Heterocyclic Carbene Ligation: Synthesis, Structure, and Their Distinct Reactivity in C–H Bond Amination Zhang, Long; Liu, Yuesheng; Deng, Liang Journal of the American Chemical Society, Vol. 136, Issue 44 https://doi.org/10.1021/ja509731z	journal	October 2014
Efficient C–H Amination Catalysis Using Nickel-Dipyrrin Complexes Dong, Yuyang; Clarke, Ryan M.; Porter, Gerard J. Journal of the American Chemical Society, Vol. 142, Issue 25 https://doi.org/10.1021/jacs.0c02126	journal	May 2020
C–H Amination Mediated by Cobalt Organoazide Adducts and the Corresponding Cobalt Nitrenoid Intermediates Baek, Yunjung; Das, Anuvab; Zheng, Shao-Liang Journal of the American Chemical Society, Vol. 142, Issue 25 https://doi.org/10.1021/jacs.0c04252	journal	May 2020
Characterization of Porphyrin-Co(III)-‘Nitrene Radical’ Species Relevant in Catalytic Nitrene Transfer Reactions Goswami, Monalisa; Lyaskovskyy, Volodymyr; Domingos, Sérgio R. Journal of the American Chemical Society, Vol. 137, Issue 16 https://doi.org/10.1021/jacs.5b01197	journal	April 2015
Two-Coordinate Co(II) Imido Complexes as Outstanding Single-Molecule Magnets Yao, Xiao-Nan; Du, Jing-Zhen; Zhang, Yi-Quan Journal of the American Chemical Society, Vol. 139, Issue 1 https://doi.org/10.1021/jacs.6b11043	journal	December 2016
Catalytic C–H Amination Mediated by Dipyrrin Cobalt Imidos Baek, Yunjung; Betley, Theodore A. Journal of the American Chemical Society, Vol. 141, Issue 19 https://doi.org/10.1021/jacs.9b01262	journal	April 2019
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
Asymmetric Induction and Enantiodivergence in Catalytic Radical C–H Amination via Enantiodifferentiative H-Atom Abstraction and Stereoretentive Radical Substitution Lang, Kai; Torker, Sebastian; Wojtas, Lukasz Journal of the American Chemical Society, Vol. 141, Issue 31 https://doi.org/10.1021/jacs.9b05850	journal	July 2019
Harnessing Secondary Coordination Sphere Interactions That Enable the Selective Amidation of Benzylic C–H Bonds Jung, Hoimin; Schrader, Malte; Kim, Dongwook Journal of the American Chemical Society, Vol. 141, Issue 38 https://doi.org/10.1021/jacs.9b07795	journal	August 2019
Direct Manipulation of Metal Imido Geometry: Key Principles to Enhance C–H Amination Efficacy Baek, Yunjung; Hennessy, Elisabeth T.; Betley, Theodore A. Journal of the American Chemical Society, Vol. 141, Issue 42 https://doi.org/10.1021/jacs.9b09015	journal	September 2019
Ligand Redox Noninnocence in [Co ^III (TAML)] ^0/– Complexes Affects Nitrene Formation van Leest, Nicolaas P.; Tepaske, Martijn A.; Oudsen, Jean-Pierre H. Journal of the American Chemical Society, Vol. 142, Issue 1 https://doi.org/10.1021/jacs.9b11715	journal	December 2019
Amidation of Saturated C−H Bonds Catalyzed by Electron-Deficient Ruthenium and Manganese Porphyrins. A Highly Catalytic Nitrogen Atom Transfer Process Yu, Xiao-Qi; Huang, Jie-Sheng; Zhou, Xiang-Ge Organic Letters, Vol. 2, Issue 15 https://doi.org/10.1021/ol000107r	journal	June 2000
Cobalt-Catalyzed Intramolecular C−H Amination with Arylsulfonyl Azides Ruppel, Joshua V.; Kamble, Rajesh M.; Zhang, X. Peter Organic Letters, Vol. 9, Issue 23 https://doi.org/10.1021/ol702265h	journal	November 2007
Syntheses and Structures of Group 14 1,3-Dimetallacyclobutanes Leung, Wing-Por; Ip, Queenie Wai-Yan; Wong, Suk-Yu Organometallics, Vol. 22, Issue 22 https://doi.org/10.1021/om0340793	journal	October 2003
Copper-Catalyzed sp ³ C–H Amination Gephart, Raymond T.; Warren, Timothy H. Organometallics, Vol. 31, Issue 22 https://doi.org/10.1021/om300840z	journal	August 2012
Catalytic C–H functionalization by metal carbenoid and nitrenoid insertion Davies, Huw M. L.; Manning, James R. Nature, Vol. 451, Issue 7177 https://doi.org/10.1038/nature06485	journal	January 2008
Earth-abundant transition metal catalysts for alkene hydrosilylation and hydroboration Obligacion, Jennifer V.; Chirik, Paul J. Nature Reviews Chemistry, Vol. 2, Issue 5 https://doi.org/10.1038/s41570-018-0001-2	journal	April 2018
Asymmetric formation of γ-lactams via C–H amidation enabled by chiral hydrogen-bond-donor catalysts Park, Yoonsu; Chang, Sukbok Nature Catalysis, Vol. 2, Issue 3 https://doi.org/10.1038/s41929-019-0230-x	journal	February 2019
Tunable catalyst-controlled syntheses of β- and γ-amino alcohols enabled by silver-catalysed nitrene transfer Ju, Minsoo; Huang, Minxue; Vine, Logan E. Nature Catalysis, Vol. 2, Issue 10 https://doi.org/10.1038/s41929-019-0339-y	journal	September 2019
Catalytic C–H functionalization by metalloporphyrins: recent developments and future directions Lu, Hongjian; Zhang, X. Peter Chem. Soc. Rev., Vol. 40, Issue 4 https://doi.org/10.1039/C0CS00070A	journal	January 2011
N-Atom transfer via thermal or photolytic activation of a Co-azido complex with a PNP pincer ligand Vreeken, V.; Baij, L.; de Bruin, B. Dalton Transactions, Vol. 46, Issue 22 https://doi.org/10.1039/C7DT01712J	journal	January 2017
Reversible dehydrogenation of a primary aryl borane MacNeil, Connor S.; Hsiang, Shou-Jen; Hayes, Paul G. Chemical Communications, Vol. 56, Issue 82 https://doi.org/10.1039/D0CC05503D	journal	January 2020
Iron-mediated C–H bond amination by organic azides on a tripodal bis(anilido)iminophosphorane platform Xiao, Jie; Deng, Liang Dalton Transactions, Vol. 42, Issue 16 https://doi.org/10.1039/c3dt50518a	journal	January 2013
633. The crystal structure of trans-dimesitylbis(diethylphenylphosphine)cobalt(II) Owston, P. G.; Rowe, J. M. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9630003411	journal	January 1963
An FeIVO complex of a tetradentate tripodal nonheme ligand Lim, M. H.; Rohde, J. -U.; Stubna, A. Proceedings of the National Academy of Sciences, Vol. 100, Issue 7 https://doi.org/10.1073/pnas.0636830100	journal	March 2003
Synthesis of a copper-supported triplet nitrene complex pertinent to copper-catalyzed amination Carsch, Kurtis M.; DiMucci, Ida M.; Iovan, Diana A. Science, Vol. 365, Issue 6458 https://doi.org/10.1126/science.aax4423	journal	September 2019

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