Snapshots of a Migrating H‐Atom: Characterization of a Reactive Iron(III) Indenide Hydride and its Nearly Isoenergetic Ring‐Protonated Iron(I) Isomer

Drover, Marcus W.; Schild, Dirk J.; Oyala, Paul H.; Peters, Jonas C.

doi:10.1002/ange.201909050

Title: Snapshots of a Migrating H‐Atom: Characterization of a Reactive Iron(III) Indenide Hydride and its Nearly Isoenergetic Ring‐Protonated Iron(I) Isomer

Journal Article · 18 September 2019 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.201909050 · OSTI ID:1562579

^[1]; Schild, Dirk J. ^[1];

^[1];

^[1]

Division of Chemistry and Chemical Engineering California Institute of Technology Pasadena CA 91125 USA

Abstract We report the characterization of an S = iron π‐complex, [Fe(η ⁶ ‐IndH)(depe)] ⁺ (Ind=Indenide (C ₉ H ₇ ⁻ ), depe=1,2‐bis(diethylphosphino)ethane), which results via C−H elimination from a transient Fe ^III hydride, [Fe(η ³ :η ² ‐Ind)(depe)H] ⁺ . Owing to weak M−H/C−H bonds, these species appear to undergo proton‐coupled electron transfer (PCET) to release H ₂ through bimolecular recombination. Mechanistic information, gained from stoichiometric as well as computational studies, reveal the open‐shell π‐arene complex to have a BDFE _C‐H value of ≈50 kcal mol ⁻¹ , roughly equal to the BDFE _Fe‐H of its Fe ^III −H precursor (Δ G °≈0 between them). Markedly, this reactivity differs from related Fe(η ⁵ ‐Cp/Cp*) compounds, for which terminal Fe ^III −H cations are isolable and have been structurally characterized, highlighting the effect of a benzannulated ring (indene). Overall, this study provides a structural, thermochemical, and mechanistic foundation for the characterization of indenide/indene PCET precursors and outlines a valuable approach for the differentiation of a ring‐ versus a metal‐bound H‐atom by way of continuous‐wave (CW) and pulse EPR (HYSCORE) spectroscopic measurements.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

OSTI ID:: 1562579

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 43 Vol. 131; ISSN 0044-8249

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

Country of Publication:: Germany

Language:: English

References (48)

Die permethylierten Elektronenüberschuß-Metallocene Kölle, Ulrich; Khouzami, Found Angewandte Chemie, Vol. 92, Issue 8 https://doi.org/10.1002/ange.19800920830	journal	August 1980
Characterization of the FeH Bond in a Three-Coordinate Terminal Hydride Complex of Iron(I) Chiang, Karen P.; Scarborough, Christopher C.; Horitani, Masaki Angewandte Chemie, Vol. 124, Issue 15 https://doi.org/10.1002/ange.201109204	journal	February 2012
Protonation of Ferrocene: A Low-Temperature X-ray Diffraction Study of [Cp ₂ FeH](PF ₆ ) Reveals an Iron-Bound Hydrido Ligand Malischewski, Moritz; Seppelt, Konrad; Sutter, Jörg Angewandte Chemie, Vol. 129, Issue 43 https://doi.org/10.1002/ange.201704854	journal	September 2017
Permethylated Electron-Excess Metallocenes Koelle, Ulrich; Khouzami, Fouad Angewandte Chemie International Edition in English, Vol. 19, Issue 8 https://doi.org/10.1002/anie.198006401	journal	August 1980
Characterization of the FeH Bond in a Three-Coordinate Terminal Hydride Complex of Iron(I) Chiang, Karen P.; Scarborough, Christopher C.; Horitani, Masaki Angewandte Chemie International Edition, Vol. 51, Issue 15 https://doi.org/10.1002/anie.201109204	journal	February 2012
Protonation of Ferrocene: A Low-Temperature X-ray Diffraction Study of [Cp ₂ FeH](PF ₆ ) Reveals an Iron-Bound Hydrido Ligand Malischewski, Moritz; Seppelt, Konrad; Sutter, Jörg Angewandte Chemie International Edition, Vol. 56, Issue 43 https://doi.org/10.1002/anie.201704854	journal	September 2017
New high yield syntheses of ruthenocene and osmocene and their decamethyl derivatives. The crystal structure of [Ru(η5-C5Me5)2] Liles, David C.; Shaver, Alan; Singleton, Eric Journal of Organometallic Chemistry, Vol. 288, Issue 2 https://doi.org/10.1016/0022-328X(85)87286-7	journal	June 1985
Studies on the reactivity of metal π-complexes Court, T. L.; Werner, H. Journal of Organometallic Chemistry, Vol. 65, Issue 2 https://doi.org/10.1016/S0022-328X(00)91276-2	journal	January 1974
Sigmatropic and haptotropic rearrangements in organometallic chemistry Gridnev, I. Coordination Chemistry Reviews, Vol. 252, Issue 15-17 https://doi.org/10.1016/j.ccr.2007.10.021	journal	August 2008
Cp*Fe(Me2PCH2CH2PMe2)(CHO): Hydride shuttle reactivity of a thermally stable formyl complex Sapsford, Joshua S.; Gates, Sarah J.; Doyle, Laurence R. Inorganica Chimica Acta, Vol. 488 https://doi.org/10.1016/j.ica.2019.01.022	journal	March 2019
Thermodynamic Hydricity of Transition Metal Hydrides Wiedner, Eric S.; Chambers, Matthew B.; Pitman, Catherine L. Chemical Reviews, Vol. 116, Issue 15 https://doi.org/10.1021/acs.chemrev.6b00168	journal	June 2016
Synthesis and Reactivity toward H ₂ of (η ⁵ -C ₅ Me ₅ )Rh(III) Complexes with Bulky Aminopyridinate Ligands Zamorano, Ana; Rendón, Nuria; Valpuesta, José E. V. Inorganic Chemistry, Vol. 54, Issue 13 https://doi.org/10.1021/acs.inorgchem.5b00905	journal	June 2015
Hydride Transfer from Iron(II) Hydride Compounds to NAD(P) ⁺ Analogues Zhang, Fanjun; Jia, Jiong; Dong, Shuli Organometallics, Vol. 35, Issue 8 https://doi.org/10.1021/acs.organomet.6b00179	journal	April 2016
Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States Evans, William J. Organometallics, Vol. 35, Issue 18 https://doi.org/10.1021/acs.organomet.6b00466	journal	September 2016
Solvent Effects on Hydride Transfer from Cp*(P-P)FeH to BNA ⁺ Cation Zhang, Fanjun; Xu, Xin; Zhao, Yingjie Organometallics, Vol. 36, Issue 7 https://doi.org/10.1021/acs.organomet.6b00907	journal	March 2017
Dehydrogenation of Dimethylamine–Borane Catalyzed by Half-Sandwich Ir and Rh Complexes: Mechanism and the Role of Cp* Noninnocence Pal, Shrinwantu; Kusumoto, Shuhei; Nozaki, Kyoko Organometallics, Vol. 37, Issue 6 https://doi.org/10.1021/acs.organomet.7b00889	journal	February 2018
Catalytic N ₂ -to-NH ₃ Conversion by Fe at Lower Driving Force: A Proposed Role for Metallocene-Mediated PCET Chalkley, Matthew J.; Del Castillo, Trevor J.; Matson, Benjamin D. ACS Central Science, Vol. 3, Issue 3 https://doi.org/10.1021/acscentsci.7b00014	journal	February 2017
Monocyclopentadienyl halide complexes of the d- and f-block elements Poli, Rinaldo. Chemical Reviews, Vol. 91, Issue 4 https://doi.org/10.1021/cr00004a004	journal	June 1991
The transition-metal-hydrogen bond Pearson, Ralph G. Chemical Reviews, Vol. 85, Issue 1 https://doi.org/10.1021/cr00065a002	journal	February 1985
Ring-slippage chemistry of transition metal cyclopentadienyl and indenyl complexes O'Connor, Joseph M.; Casey, Charles P. Chemical Reviews, Vol. 87, Issue 2 https://doi.org/10.1021/cr00078a002	journal	April 1987
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
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
Hydrogenation of pentacyanocobaltate(II) at high pressures Halpern, Jack; Pribanic, Marijan Inorganic Chemistry, Vol. 9, Issue 11 https://doi.org/10.1021/ic50093a057	journal	November 1970
Hydricity of an Fe–H Species and Catalytic CO ₂ Hydrogenation Fong, Henry; Peters, Jonas C. Inorganic Chemistry, Vol. 54, Issue 11 https://doi.org/10.1021/ic502508p	journal	December 2014
Organotransition-metal metallacarboranes. 19. Indenyliron(II) and -iron(III) complexes and related species. .eta.6 .fwdarw. .eta.5 Haptotropic rearrangement, electrochemistry, and polyhedral expansion of (arene)Fe(Et2C2B4H4) clusters Fessenbecker, Achim; Stephan, Martin; Grimes, Russell N. Journal of the American Chemical Society, Vol. 113, Issue 8 https://doi.org/10.1021/ja00008a039	journal	April 1991
Activation of methane and toluene by rhodium(II) porphyrin complexes Wayland, Bradford B.; Ba, Sujuan; Sherry, Alan E. Journal of the American Chemical Society, Vol. 113, Issue 14 https://doi.org/10.1021/ja00014a025	journal	July 1991
Methyl effects on the basicities of cyclopentadienide and indenide ions and on the chemistry of their transition metal complexes Bordwell, Frederick G.; Bausch, Mark J. Journal of the American Chemical Society, Vol. 105, Issue 19 https://doi.org/10.1021/ja00357a057	journal	September 1983
Protonation of Metallocenes by Strong Acids. Structure of the Cation Curphey, T. J.; Santer, J. O.; Rosenblum, M. Journal of the American Chemical Society, Vol. 82, Issue 19 https://doi.org/10.1021/ja01504a062	journal	October 1960
Hydricities of BzNADH, C ₅ H ₅ Mo(PMe ₃ )(CO) ₂ H, and C ₅ Me ₅ Mo(PMe ₃ )(CO) ₂ H in Acetonitrile Ellis, William W.; Raebiger, James W.; Curtis, Calvin J. Journal of the American Chemical Society, Vol. 126, Issue 9 https://doi.org/10.1021/ja038567d	journal	March 2004
Thermodynamic Hydricities of Biomimetic Organic Hydride Donors Ilic, Stefan; Pandey Kadel, Usha; Basdogan, Yasemin Journal of the American Chemical Society, Vol. 140, Issue 13 https://doi.org/10.1021/jacs.7b13526	journal	March 2018
Fe-Mediated Nitrogen Fixation with a Metallocene Mediator: Exploring p K _a Effects and Demonstrating Electrocatalysis Chalkley, Matthew J.; Del Castillo, Trevor J.; Matson, Benjamin D. Journal of the American Chemical Society, Vol. 140, Issue 19 https://doi.org/10.1021/jacs.8b02335	journal	April 2018
An S = ¹ / ₂ Iron Complex Featuring N ₂ , Thiolate, and Hydride Ligands: Reductive Elimination of H ₂ and Relevant Thermochemical Fe–H Parameters Gu, Nina X.; Oyala, Paul H.; Peters, Jonas C. Journal of the American Chemical Society, Vol. 140, Issue 20 https://doi.org/10.1021/jacs.8b02603	journal	April 2018
Base-Promoted, Remote C–H Activation at a Cationic (η ⁵ -C ₅ Me ₅ )Ir(III) Center Involving Reversible C–C Bond Formation of Bound C ₅ Me ₅ Moreno, Juan J.; Espada, María F.; Campos, Jesús Journal of the American Chemical Society, Vol. 141, Issue 6 https://doi.org/10.1021/jacs.8b11752	journal	January 2019
Cp* Noninnocence Leads to a Remarkably Weak C–H Bond via Metallocene Protonation Chalkley, Matthew J.; Oyala, Paul H.; Peters, Jonas C. Journal of the American Chemical Society, Vol. 141, Issue 11 https://doi.org/10.1021/jacs.9b00193	journal	February 2019
Stabilization of 16-Electron Paramagnetic Organoiron Species versus Coordination of Dinitrogen. X-ray Crystal Structures of [Fe(.eta.5-C5H5)(N2)(dippe)][BPh4], [Fe(.eta.5-C5Me5)(dippe)][BPh4], and [Fe(.eta.5-C5H5)Cl(dippe)][BPh4] (dippe = 1,2-Bis(diisopropylphosphino)ethane) Leal, Auxiliadora de la Jara; Tenorio, Manuel Jimenez; Puerta, M. Carmen Organometallics, Vol. 14, Issue 8 https://doi.org/10.1021/om00008a035	journal	August 1995
Protonation of η ⁵ -Indenyl Ruthenium Hydride Complexes (η ⁵ -C ₉ H ₇ )Ru(L ₂ )H and η ⁵ −η ⁶ Haptotropic Rearrangement. X-ray Crystal Structures of (η ⁵ -C ₉ H ₇ )Ru(dppm)H and [(η ⁶ -C ₉ H ₈ )Ru(dppp)H] ⁺ Hung, Mei Yuen; Ng, Siu Man; Zhou, Zhongyuan Organometallics, Vol. 19, Issue 18 https://doi.org/10.1021/om000266e	journal	September 2000
Novel diamagnetic and paramagnetic iron(II), iron(III), and iron(IV) classical and nonclassical hyrides. X-ray crystal structure of [Fe(C5Me5)(dppe)D]PF6 Hamon, Paul; Toupet, Loic; Hamon, Jean Rene Organometallics, Vol. 11, Issue 4 https://doi.org/10.1021/om00040a001	journal	April 1992
Haptotropic Shifts in Cyclopentadienyl Organometallic Complexes: Ring Folding vs Ring Slippage Veiros, Luis F. Organometallics, Vol. 19, Issue 26 https://doi.org/10.1021/om000589a	journal	December 2000
Control of slippage and conformation in indenyl complexes Faller, J. W.; Crabtree, R. H.; Habib, A. Organometallics, Vol. 4, Issue 5 https://doi.org/10.1021/om00124a022	journal	May 1985
Trends in Cyclopentadienyl−Main-Group-Metal Bonding ^† Budzelaar, Peter H. M.; Engelberts, Jeroen J.; van Lenthe, Joop H. Organometallics, Vol. 22, Issue 8 https://doi.org/10.1021/om020928v	journal	April 2003
Thermal Dihydrogen Elimination from Cp* ₂ Yb(4,5-diazafluorene) Nocton, Grégory; Booth, Corwin H.; Maron, Laurent Organometallics, Vol. 32, Issue 5 https://doi.org/10.1021/om300876b	journal	November 2012
Activation of a C−H Bond in Indene by [(COD)Rh(μ ₂ -OH)] ₂ ^† Bercaw, John E.; Hazari, Nilay; Labinger, Jay A. Organometallics, Vol. 28, Issue 18 https://doi.org/10.1021/om9004498	journal	September 2009
Cyclopentadiene-mediated hydride transfer from rhodium complexes Pitman, C. L.; Finster, O. N. L.; Miller, A. J. M. Chemical Communications, Vol. 52, Issue 58 https://doi.org/10.1039/C6CC00575F	journal	January 2016
Reversible coordination of N ₂ and H ₂ to a homoleptic S = 1/2 Fe( i ) diphosphine complex in solution and the solid state Doyle, Laurence R.; Scott, Daniel J.; Hill, Peter J. Chemical Science, Vol. 9, Issue 37 https://doi.org/10.1039/C8SC01841C	journal	January 2018
Cp* Chemistry of main-group elements † Jutzi, Peter; Reumann, Guido Journal of the Chemical Society, Dalton Transactions, Issue 14 https://doi.org/10.1039/b001365j	journal	January 2000
Isolation and characterization of a cationic 19-electron iron(III) hydride complex; electron transfer induced hydride migration by carbon monoxide at an iron(III) centre Hamon, Paul; Hamon, Jean-Ren�; Lapinte, Claude Journal of the Chemical Society, Chemical Communications, Issue 21 https://doi.org/10.1039/c39920001602	journal	January 1992
Iron(0) arene and iron(II) hydride complexes from the hydrogenation or thermolysis of high-spin iron(II) alkyls Hermes, Ann R.; Warren, Timothy H.; Girolami, Gregory S. Journal of the Chemical Society, Dalton Transactions, Issue 2 https://doi.org/10.1039/dt9950000301	journal	January 1995
Proton–hydride tautomerism in hydrogen evolution catalysis Quintana, Luis M. Aguirre; Johnson, Samantha I.; Corona, Sydney L. Proceedings of the National Academy of Sciences, Vol. 113, Issue 23 https://doi.org/10.1073/pnas.1606018113	journal	May 2016

Similar Records

Snapshots of a Migrating H‐Atom: Characterization of a Reactive Iron(III) Indenide Hydride and its Nearly Isoenergetic Ring‐Protonated Iron(I) Isomer

Journal Article · 2019 · Angewandte Chemie (International Edition) · OSTI ID:1562575

Drover, Marcus W.; Schild, Dirk J.; Oyala, Paul H.; +1 more

Generating Potent C–H PCET Donors: Ligand-Induced Fe-to-Ring Proton Migration from a Cp*Fe^III–H Complex Demonstrates a Promising Strategy

Journal Article · 2020 · Journal of the American Chemical Society · OSTI ID:1710227

Schild, Dirk J.; Drover, Marcus W.; Oyala, Paul H.; +1 more

The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase

Journal Article · 2019 · Angewandte Chemie · OSTI ID:1492741

Yang, Guoju; Akhade, Sneha A.; Chen, Xi; +5 more

Title: Snapshots of a Migrating H‐Atom: Characterization of a Reactive Iron(III) Indenide Hydride and its Nearly Isoenergetic Ring‐Protonated Iron(I) Isomer

Citation Formats

References (48)

Similar Records

Related Subjects