The underappreciated influence of ancillary halide on metal–ligand proton tautomerism

Jain, Anant Kumar; Gau, Michael R.; Carroll, Patrick J.; Goldberg, Karen I.

doi:10.1039/D2SC00279E

Title: The underappreciated influence of ancillary halide on metal–ligand proton tautomerism

Journal Article · Wed Jul 06 00:00:00 EDT 2022 · Chemical Science

DOI:https://doi.org/10.1039/D2SC00279E· OSTI ID:1873017

^[1]; Gau, Michael R. ^[1]; Carroll, Patrick J. ^[1];

^[1]

Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania, 19104, USA

Syntheses of Vaska-type complexes [IrP₂X(CO)] (P = phosphine, X = halide) with all four common halides (fluoride, chloride, bromide, and iodide) was attempted using a protic and hemilabile imidazolyl di-tert-butyl phosphine ligand. In the solid-state, all four complexes were found to be ionic with the halides in the outer-sphere, and the fourth coordination site of the square plane occupied by the imidazole arm of the ligand. In solution, however, the chloride complex was found to be in equilibrium with an octahedral Ir^III–H species at room temperature. For the bromide and iodide analogs, the corresponding Ir^III–H species were also observed but only after heating the solutions. The neutral IrI Vaska's analogs for X = Cl, Br, and I were obtained upon addition of excess halide salt, albeit heating was required for X = Br and I. The Ir^III–H species are proposed to originate from tautomerization of minor amounts of the electron rich neutral Vaska analog (halide inner-sphere and phosphines monodentate) that are in equilibrium with the ionic species. Heating is required for the larger anions of bromide and iodide to overcome a kinetic barrier associated with their movement to an inner-sphere position prior to tautormerization. For the fluoride analog, the Ir^III–H was not observed, attributable to strong hydrogen bonding interactions of the imidazolyl proton with the fluoride anion.

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Research Organization:: Univ. of Pennsylvania, Philadelphia, PA (United States)

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

Grant/Contract Number:: SC0018057; CHE-0650456; CHE-1827457

OSTI ID:: 1873017

Alternate ID(s):: OSTI ID: 1873476

Journal Information:: Chemical Science, Journal Name: Chemical Science Vol. 13 Journal Issue: 26; ISSN 2041-6520

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

References (52)

Metal–Ligand Cooperation by Aromatization–Dearomatization: A New Paradigm in Bond Activation and “Green” Catalysis Gunanathan, Chidambaram; Milstein, David Accounts of Chemical Research, Vol. 44, Issue 8 https://doi.org/10.1021/ar2000265	journal	August 2011
The Importance of Steric Factors in Iridium Pincer Complexes Goldberg, Jonathan M.; Wong, Gene W.; Brastow, Kenzie E. Organometallics, Vol. 34, Issue 4 https://doi.org/10.1021/om501166w	journal	February 2015
Anion control of tautomeric equilibria: Fe–H vs. N–H influenced by NH⋯F hydrogen bonding Chambers, Geoffrey M.; Johnson, Samantha I.; Raugei, Simone Chemical Science, Vol. 10, Issue 5 https://doi.org/10.1039/C8SC04239J	journal	January 2019
Multimodal Study of Secondary Interactions in Cp*Ir Complexes of Imidazolylphosphines Bearing an NH Group Grotjahn, Douglas B.; Kraus, John E.; Amouri, Hani Journal of the American Chemical Society, Vol. 132, Issue 23 https://doi.org/10.1021/ja906712g	journal	May 2010
Hydrogen-bonded nickel( i ) complexes Wilson, Jessica R.; Zeller, Matthias; Szymczak, Nathaniel K. Chemical Communications, Vol. 57, Issue 6 https://doi.org/10.1039/D0CC07216H	journal	January 2021
Stabilization of Nickel Complexes with Ni ⁰ ···H–N Bonding Interactions Using Sterically Demanding Cyclic Diphosphine Ligands Wiedner, Eric S.; Yang, Jenny Y.; Chen, Shentan Organometallics, Vol. 31, Issue 1 https://doi.org/10.1021/om200709z	journal	December 2011
Hydrogen Bonds Dictate the Coordination Geometry of Copper: Characterization of a Square‐Planar Copper(I) Complex Dahl, Eric W.; Szymczak, Nathaniel K. Angewandte Chemie International Edition, Vol. 55, Issue 9 https://doi.org/10.1002/anie.201511527	journal	January 2016
The trans influence of F, Cl, Br and I ligands in a series of square-planar Pd(II) complexes. Relative affinities of halide anions for the metal centre in trans-[(Ph3P)2Pd(Ph)X] Flemming, Jeffrey P.; Pilon, Mark C.; Borbulevitch, Oleg Ya. Inorganica Chimica Acta, Vol. 280, Issue 1-2 https://doi.org/10.1016/S0020-1693(98)00055-3	journal	October 1998
Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides Schilter, David; Camara, James M.; Huynh, Mioy T. Chemical Reviews, Vol. 116, Issue 15 https://doi.org/10.1021/acs.chemrev.6b00180	journal	June 2016
Changes in Coordination of Sterically Demanding Hybrid Imidazolylphosphine Ligands on Pd(0) and Pd(II) Grotjahn, Douglas B.; Gong, Yi; Zakharov, Lev Journal of the American Chemical Society, Vol. 128, Issue 2 https://doi.org/10.1021/ja054779u	journal	December 2005
Revealing the halide effect on the kinetics of the aerobic oxidation of Cu( i ) to Cu( ii ) Deng, Yi; Zhang, Guanghui; Qi, Xiaotian Chemical Communications, Vol. 51, Issue 2 https://doi.org/10.1039/C4CC05720A	journal	January 2015
Stereodynamics of trans-[tert-C4H9)2PR]2M(CO)X systems (R = H, CH3; M = Rh(I), Ir(I); X = Cl, Br, I). Assignment of conformational preferences and conformational exchange itineraries Bushweller, C. Hackett; Rithner, Christopher D.; Butcher, David J. Inorganic Chemistry, Vol. 25, Issue 10 https://doi.org/10.1021/ic00230a019	journal	May 1986
The synthesis and crystallographic characterisation of the complexes [RuX(CO)(η2-C,N-C6H5C(H)NC6H4-4Me)(PPh3)2]·CHCl3 (X=Cl, Br, I, F): Evidence for competing Ru–X⋯Cl–CHCl2 and Ru–X⋯HCCl3 interactions in the solid state Flower, Kevin R.; Leal, Laura G.; Pritchard, Robin G. Journal of Organometallic Chemistry, Vol. 690, Issue 14 https://doi.org/10.1016/j.jorganchem.2005.04.026	journal	July 2005
Iridium Chemistry of 1,6-Bis(( tert -butylphosphino)methyl)-1,3,5-cycloheptatriene Nemeh, Saad; Flesher, Robert J.; Gierling, Karlheinz Organometallics, Vol. 17, Issue 10 https://doi.org/10.1021/om980045x	journal	April 1998
Dihydroperimidine-Derived N-Heterocyclic Pincer Carbene Complexes via Double C–H Activation Hill, Anthony F.; McQueen, Caitlin M. A. Organometallics, Vol. 31, Issue 23 https://doi.org/10.1021/om300897w	journal	November 2012
Syntheses of PBP Pincer Iridium Complexes: A Supporting Boryl Ligand Segawa, Yasutomo; Yamashita, Makoto; Nozaki, Kyoko Journal of the American Chemical Society, Vol. 131, Issue 26 https://doi.org/10.1021/ja9037092	journal	June 2009
Experimental and DFT Investigations Reveal the Influence of the Outer Coordination Sphere on the Vibrational Spectra of Nickel-Substituted Rubredoxin, a Model Hydrogenase Enzyme Slater, Jeffrey W.; Marguet, Sean C.; Cirino, Sabrina L. Inorganic Chemistry, Vol. 56, Issue 7 https://doi.org/10.1021/acs.inorgchem.6b02934	journal	March 2017
Aromaticity in catalysis: metal ligand cooperation via ligand dearomatization and rearomatization Gonçalves, Théo P.; Dutta, Indranil; Huang, Kuo-Wei Chemical Communications, Vol. 57, Issue 25 https://doi.org/10.1039/D1CC00528F	journal	January 2021
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
Aza- and Oxadithiolates Are Probable Proton Relays in Functional Models for the [FeFe]-Hydrogenases Barton, Bryan E.; Olsen, Matthew T.; Rauchfuss, Thomas B. Journal of the American Chemical Society, Vol. 130, Issue 50 https://doi.org/10.1021/ja8057666	journal	December 2008
Synthesis, Reactivity and Structures of Iridium Tetrafluoropyridyl Complexes: Ammonia Coordination and Activation Jungton, Ann-Katrin; Kläring, Paul; Braun, Thomas Zeitschrift für anorganische und allgemeine Chemie, Vol. 638, Issue 3-4 https://doi.org/10.1002/zaac.201100440	journal	February 2012
Electron‐Rich Vaska‐Type Complexes trans ‐[Ir(CO)Cl(2‐Ph ₂ PC ₆ H ₄ COOMe) ₂ ] and trans ‐[Ir(CO)Cl(2‐Ph ₂ PC ₆ H ₄ OMe) ₂ ]: Synthesis, Characterisation and Reactivity Dutta, Dipak Kumar; Deb, Biswajit; Sarmah, Bhaskar Jyoti European Journal of Inorganic Chemistry, Vol. 2011, Issue 6 https://doi.org/10.1002/ejic.201001005	journal	January 2011
Reaction of the fluoride anion with acetonitrile. Chloroform and methylene chloride Christe, Karl O.; Wilson, William W. Journal of Fluorine Chemistry, Vol. 47, Issue 1 https://doi.org/10.1016/S0022-1139(00)80453-4	journal	April 1990
PC(sp ³ )P pincer carbonyl complexes of iridium( i ), and iridium( iii ) Jonasson, Klara J.; Polukeev, Alexey V.; Wendt, Ola F. RSC Advances, Vol. 5, Issue 20 https://doi.org/10.1039/C4RA15562A	journal	January 2015
Role of Phosphine Sterics in Strained Aminophosphine Chelate Formation Bowes, Eric G.; Beattie, D. Dawson; Love, Jennifer A. Inorganic Chemistry, Vol. 58, Issue 5 https://doi.org/10.1021/acs.inorgchem.8b03514	journal	February 2019
Noncoordinating Anions—Fact or Fiction? A Survey of Likely Candidates Krossing, Ingo; Raabe, Ines Angewandte Chemie International Edition, Vol. 43, Issue 16 https://doi.org/10.1002/anie.200300620	journal	April 2004
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
Complexes derived from the reactions of diphenylphosphinoacetic acid. Kuang, Shan-Ming; Edwards, Dennis A.; Fanwick, Phillip E. Inorganica Chimica Acta, Vol. 343 https://doi.org/10.1016/S0020-1693(02)01190-8	journal	January 2003
Formation of an iridium σ-cyclopropane complex by the intramolecular activation of a cyclopropylphosphine: Rearrangement to a chelating σ-vinyl complex Youngs, Wiley J.; Simms, Barbara L.; Ibers, James A. Journal of Organometallic Chemistry, Vol. 272, Issue 2 https://doi.org/10.1016/0022-328X(84)80472-6	journal	September 1984
A Synthetic Nickel Electrocatalyst with a Turnover Frequency Above 100,000 s^-1 for H₂ Production Helm, M. L.; Stewart, M. P.; Bullock, R. M. Science, Vol. 333, Issue 6044, p. 863-866 https://doi.org/10.1126/science.1205864	journal	August 2011
Synthesis, Structure and Reactivity of Iridium Hydrido Fluorido Complexes Kläring, Paul; Jungton, Ann‐Katrin; Braun, Thomas European Journal of Inorganic Chemistry, Vol. 2012, Issue 9 https://doi.org/10.1002/ejic.201100917	journal	December 2011
Preparation and Reactivity of Bimetallic (pincer)Ir Complexes Goldberg, Jonathan M.; Guard, Louise M.; Wong, Gene W. Organometallics, Vol. 39, Issue 18 https://doi.org/10.1021/acs.organomet.0c00403	journal	September 2020
Nature of hydrogen interactions with Ni(II) complexes containing cyclic phosphine ligands with pendant nitrogen bases Wilson, A. D.; Shoemaker, R. K.; Miedaner, A. Proceedings of the National Academy of Sciences, Vol. 104, Issue 17 https://doi.org/10.1073/pnas.0608928104	journal	March 2007
Studies on carbon-hydrogen activation. 7. Carbon-hydrogen activation of ethene by non-cyclopentadienyl-containing iridium complexes. Supporting role of iPr2PCH2CH2OMe as phosphine ligand Schulz, Michael; Werner, Helmut Organometallics, Vol. 11, Issue 8 https://doi.org/10.1021/om00044a017	journal	August 1992
Mono- and Dinuclear Binding Modes of the 2,5-Bis(α-pyridyl)pyrrolate Ligand in Platinum(II) Complexes Newman, Drew C.; Gau, Michael R.; Carroll, Patrick J. Organometallics, Vol. 40, Issue 12 https://doi.org/10.1021/acs.organomet.1c00152	journal	June 2021
Acceptor PCP Pincer Iridium Chemistry: ( ^{CF ₃} PCP)Ir ^III Coordination Properties Adams, Jeramie J.; Lau, Ade; Arulsamy, Navamoney Organometallics, Vol. 30, Issue 4 https://doi.org/10.1021/om1008633	journal	February 2011
Understanding the Behavior of Halogens as Hydrogen Bond Acceptors Brammer, Lee; Bruton, Eric A.; Sherwood, Paul Crystal Growth & Design, Vol. 1, Issue 4 https://doi.org/10.1021/cg015522k	journal	July 2001
Iridium PC(sp ³ )P Pincer Complexes with Hemilabile Pendant Arms: Synthesis, Characterization, and Catalytic Activity De-Botton, Sophie; Cohen, Shirel; Gelman, Dmitri Organometallics, Vol. 37, Issue 8 https://doi.org/10.1021/acs.organomet.8b00105	journal	April 2018
Mechanistic Insights into Catalytic H ₂ Oxidation by Ni Complexes Containing a Diphosphine Ligand with a Positioned Amine Base Yang, Jenny Y.; Bullock, R. Morris; Shaw, Wendy J. Journal of the American Chemical Society, Vol. 131, Issue 16 https://doi.org/10.1021/ja900483x	journal	April 2009
New Shapes of PC(sp ³ )P Pincer Complexes Azerraf, Clarite; Gelman, Dmitri Organometallics, Vol. 28, Issue 22 https://doi.org/10.1021/om900723s	journal	October 2009
Role of Ligand Protonation in Dihydrogen Evolution from a Pentamethylcyclopentadienyl Rhodium Catalyst Johnson, Samantha I.; Gray, Harry B.; Blakemore, James D. Inorganic Chemistry, Vol. 56, Issue 18 https://doi.org/10.1021/acs.inorgchem.7b01698	journal	September 2017
Quantifying the Donor Strength of Ligand-Stabilized Main Group Fragments Maser, Leon; Schneider, Christian; Vondung, Lisa Journal of the American Chemical Society, Vol. 141, Issue 18 https://doi.org/10.1021/jacs.9b02598	journal	April 2019
Bifunctional Imidazolylphosphine Ligands as Hydrogen Bond Donors Promote N−H and O−H Activation on Platinum Grotjahn, Douglas B.; Gong, Yi; DiPasquale, Antonio G. Organometallics, Vol. 25, Issue 24 https://doi.org/10.1021/om060880b	journal	October 2006
Favored C?H Activation in Comparison to Cyclopropyl C?C Activation using a Vaska-Analogous Complex Ruhland, Klaus; Herdtweck, Eberhardt Advanced Synthesis & Catalysis, Vol. 347, Issue 2-3 https://doi.org/10.1002/adsc.200404257	journal	February 2005
Iodide effects in transition metal catalyzed reactions Maitlis, Peter M.; Haynes, Anthony; James, Brian R. Dalton Transactions, Issue 21 https://doi.org/10.1039/b410128f	journal	January 2004
Kinetics of phosphine substitution in CpRu(PPh ₃ ) ₂ X (X = Cl, Br, I, N ₃ , and NCO) Hill, David; Delaney, Connor; Clark, Miles RSC Advances, Vol. 7, Issue 55 https://doi.org/10.1039/C7RA02793A	journal	January 2017
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
Synthesis, X‐Ray Structure and Complexation Behavior of the New Tripodal Phosphane Ligand cis, cis ‐1,3,5‐Tris[(diphenylphosphanyl)methyl]1‐1,3,5‐trimethylcyclohexane (tdppmtmcy). Crystal Structure of Ir(tdppmtmcy)(CO)Cl Mayer, Hermann A.; Fawzi, Riad; Steimann, Manfred Chemische Berichte, Vol. 126, Issue 6 https://doi.org/10.1002/cber.19931260612	journal	June 1993
Halide Effects in Transition Metal Catalysis Fagnou, Keith; Lautens, Mark Angewandte Chemie International Edition, Vol. 41, Issue 1 https://doi.org/10.1002/1521-3773(20020104)41:1<26::AID-ANIE26>3.0.CO;2-9	journal	January 2002
Molekülstruktur von bromo-carbonyl-hydrido-phenyl-bis (triäthylphosphin)iridium(III), [Ir(H)(Br)(C6H5)(CO)(PEt3)2] Behrens, U.; Dahlenburg, L. Journal of Organometallic Chemistry, Vol. 116, Issue 1 https://doi.org/10.1016/S0022-328X(00)87201-0	journal	August 1976
A Functional [NiFe]-Hydrogenase Model Compound That Undergoes Biologically Relevant Reversible Thiolate Protonation Weber, Katharina; Krämer, Tobias; Shafaat, Hannah S. Journal of the American Chemical Society, Vol. 134, Issue 51 https://doi.org/10.1021/ja309563p	journal	December 2012
Synthetic Models for the Active Site of the [FeFe]-Hydrogenase: Catalytic Proton Reduction and the Structure of the Doubly Protonated Intermediate Carroll, Maria E.; Barton, Bryan E.; Rauchfuss, Thomas B. Journal of the American Chemical Society, Vol. 134, Issue 45 https://doi.org/10.1021/ja309216v	journal	November 2012

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