Reversible Heterolytic Cleavage of the H-H Bond by Molybdenum Complexes: Controlling the Dynamics of Exchange Between Proton and Hydride

Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris

doi:10.1021/jacs.7b03053

Title: Reversible Heterolytic Cleavage of the H-H Bond by Molybdenum Complexes: Controlling the Dynamics of Exchange Between Proton and Hydride

Journal Article · Thu May 18 00:00:00 EDT 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b03053· OSTI ID:1364010

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Controlling the heterolytic cleavage of the H-H bond of dihydrogen is critically important in catalytic hydrogenations and in the catalytic oxidation of H2. We show how the rate of reversible heterolytic cleavage of H2 can be controlled over nearly four orders of magnitude at 25 °C, from 2.1 × 103 s-1 to ≥107 s-1. Bifunctional Mo complexes, [CpMo(CO)(κ3-P2N2)]+ (P2N2 = 1,5-diaza-3,7-diphosphacyclooctane with alkyl/aryl groups on N and P), have been developed for heterolytic cleavage of H2 into a proton and a hydride, akin to Frustrated Lewis Pairs. The H-H bond cleavage is enabled by the basic amine in the second coordination sphere. The products of heterolytic cleavage of H2, Mo hydride complexes bearing protonated amines, [CpMo(H)(CO)(P2N2H)]+, were characterized by spectroscopic studies and by X-ray crystallography. Variable temperature 1H, 15N and 2-D 1H-1H ROESY NMR spectra indicated rapid exchange of the proton and hydride. The exchange rates are in the order [CpMo(H)(CO)(PPh2NPh2H)]+ > [CpMo(H)(CO)(PtBu2NPh2H)]+ > [CpMo(H)(CO)(PPh2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NtBu2H)]+. The pKa values determined in acetonitrile range from 9.3 to 17.7, and show a linear correlation with the logarithm of the exchange rates. Thus the exchange dynamics are controlled through the relative acidity of the [CpMo(H)(CO)(P2N2H)]+ and [CpMo(H2)(CO)(P2N2)]+ isomers, providing a design principle for controlling heterolytic cleavage of H2.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

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

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1364010

Report Number(s):: PNNL-SA-125042; KC0302010

Journal Information:: Journal of the American Chemical Society, Vol. 139, Issue 21; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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A New Intermolecular Interaction: UnconventionalHydrogen Bonds with Element−Hydride Bonds as ProtonAcceptor Crabtree, Robert H.; Siegbahn, Per E. M.; Eisenstein, Odile Accounts of Chemical Research, Vol. 29, Issue 7 https://doi.org/10.1021/ar950150s	journal	January 1996
Complexation of an amide to iridium via an iminol tautomer and evidence Ir–H ⋯ H–O hydrogen bond Lee, Jesse C.; Rheingold, Arnold L.; Muller, Beat J. Chem. Soc., Chem. Commun., Issue 8 https://doi.org/10.1039/C39940001021	journal	January 1994
A new type of intramolecular H ⋯ H ⋯ H interaction involving N–H ⋯ H(Ir)⋯ H–N atoms. Crystal and molecular structure of [IrH(η ¹ -SC ₅ H ₄ NH) ₂ (η ² -SC ₅ H ₄ N)(PCy ₃ )]BF ₄ ·0.72CH ₂ Cl ₂ Park, Sunghan; Ramachandran, Ravindranath; Lough, Alan J. J. Chem. Soc., Chem. Commun., Issue 19 https://doi.org/10.1039/C39940002201	journal	January 1994
Competition between NH···HIr Intramolecular Proton−Hydride Interactions and NH···FBF ₃ ^- or NH···O Intermolecular Hydrogen Bonds Involving [IrH(2-thiazolidinethione) ₄ (PCy ₃ )](BF ₄ ) ₂ and Related Complexes Xu, Wei; Lough, Alan J.; Morris, Robert H. Inorganic Chemistry, Vol. 35, Issue 6 https://doi.org/10.1021/ic950997k	journal	January 1996
Iridium(III) Complex Containing a Unique Bifurcated Hydrogen Bond Interaction Involving Ir−H···H(N)···F−B atoms. Crystal and Molecular Structure of [IrH(η ¹ -SC ₅ H ₄ NH)(η ² -SC ₅ H ₄ N)(PPh ₃ ) ₂ ](BF ₄ )·0.5C ₆ H ₆ Park, Sunghan; Lough, Alan J.; Morris, Robert H. Inorganic Chemistry, Vol. 35, Issue 10 https://doi.org/10.1021/ic950438d	journal	January 1996
Facile Ru−H ₂ Heterolytic Activation and Intramolecular Proton Transfer Assisted by Basic N-Centers in the Ligands Jalón, Félix A.; Manzano, Blanca R.; Caballero, Agustín Journal of the American Chemical Society, Vol. 127, Issue 44 https://doi.org/10.1021/ja055116f	journal	November 2005
A Proton-Switchable Bifunctional Ruthenium Complex That Catalyzes Nitrile Hydroboration Geri, Jacob B.; Szymczak, Nathaniel K. Journal of the American Chemical Society, Vol. 137, Issue 40 https://doi.org/10.1021/jacs.5b08406	journal	September 2015
Synthesis, Structure, and Reactivity of Monomeric Titanocene Sulfido and Disulfide Complexes. Reaction of H ₂ with a Terminal MS Bond Sweeney, Zachary K.; Polse, Jennifer L.; Andersen, Richard A. Journal of the American Chemical Society, Vol. 119, Issue 19 https://doi.org/10.1021/ja970168t	journal	May 1997

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Interaction of Metal Oxido Compounds with B(C ₆ F ₅ ) ₃ Zwettler, Niklas; Mösch‐Zanetti, Nadia C. Chemistry – A European Journal, Vol. 25, Issue 24 https://doi.org/10.1002/chem.201805148	journal	February 2019
Parallels between Metal‐Ligand Cooperativity and Frustrated Lewis Pairs Habraken, Evi R. M.; Jupp, Andrew R.; Brands, Maria B. European Journal of Inorganic Chemistry, Vol. 2019, Issue 19 https://doi.org/10.1002/ejic.201900169	journal	May 2019
Ligand-Based Storage of Protons and Electrons in Dihydrazonopyrrole Complexes of Nickel Chang, Mu-Chieh; McNeece, Andrew J.; Hill, Ethan A. Chemistry - A European Journal, Vol. 24, Issue 31 https://doi.org/10.1002/chem.201800658	journal	May 2018
Heterolytic Si−H Bond Cleavage at a Molybdenum-Oxido-Based Lewis Pair Zwettler, Niklas; Walg, Simon P.; Belaj, Ferdinand Chemistry - A European Journal, Vol. 24, Issue 28 https://doi.org/10.1002/chem.201801677	journal	May 2018
MoIV3-Polyoxomolybdates with frustrated Lewis pairs for high-performance hydrogenation catalysis Luo, Benlong; Sang, Ruili; Lin, Lifang Catalysis Science & Technology, Vol. 9, Issue 1 https://doi.org/10.1039/c8cy01771a	journal	January 2019
Accelerating proton-coupled electron transfer of metal hydrides in catalyst model reactions Liu, Tianfei; Guo, Meiyuan; Orthaber, Andreas Nature Chemistry, Vol. 10, Issue 8 https://doi.org/10.1038/s41557-018-0076-x	journal	July 2018
Reversible Dihydrogen Activation and Hydride Transfer by a Uranium Nitride Complex Falcone, Marta; Poon, Lok Nga; Fadaei Tirani, Farzaneh Angewandte Chemie International Edition, Vol. 57, Issue 14 https://doi.org/10.1002/anie.201800203	journal	March 2018
Heterolytic Si−H Bond Cleavage at a Molybdenum-Oxido-Based Lewis Pair Zwettler, Niklas; Walg, Simon P.; Belaj, Ferdinand Chemistry - A European Journal, Vol. 24, Issue 28 https://doi.org/10.1002/chem.201800226	journal	April 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
hydrogen
heterolytic
kinetics

CCDC 1564611: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj3bn The current record is supplemented by this dataset	dataset	January 2017
CCDC 1564614: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj3fr The current record is supplemented by this dataset	dataset	January 2017
CCDC 1564615: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj3gs The current record is supplemented by this dataset	dataset	January 2017
CCDC 1564616: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj3ht The current record is supplemented by this dataset	dataset	January 2017
CCDC 1564612: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj3cp The current record is supplemented by this dataset	dataset	January 2017
CCDC 1564613: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj3dq The current record is supplemented by this dataset	dataset	January 2017
CCDC 1564607: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj36j The current record is supplemented by this dataset	dataset	January 2017
CCDC 1564608: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj37k The current record is supplemented by this dataset	dataset	January 2017
CCDC 1564609: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj38l The current record is supplemented by this dataset	dataset	January 2017
CCDC 1564610: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj39m The current record is supplemented by this dataset	dataset	January 2017
CCDC 1564604: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj33f The current record is supplemented by this dataset	dataset	January 2017
CCDC 1564605: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj34g The current record is supplemented by this dataset	dataset	January 2017
CCDC 1564606: Experimental Crystal Structure Determination Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris https://doi.org/10.5517/ccdc.csd.cc1pj35h The current record is supplemented by this dataset	dataset	January 2017