Electrostatics Generated by a Supramolecular Capsule Stabilizes the Transition State for Carbon–Carbon Reductive Elimination from Gold(III) Complex

Vaissier Welborn, Valerie; Head-Gordon, Teresa

doi:10.1021/acs.jpclett.8b01710

Title: Electrostatics Generated by a Supramolecular Capsule Stabilizes the Transition State for Carbon–Carbon Reductive Elimination from Gold(III) Complex

Journal Article · Mon Jun 25 00:00:00 EDT 2018 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.8b01710· OSTI ID:1532332

^[1];

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division

Tetrahedral assemblies of stoichiometry M₄L₆have been proven to catalyze a range of chemical reactions including the carbon-carbon reductive elimination reaction from transition metals such as gold. Here, we perform quantum chemical calculations of Gold(III) transition metal complexes in vacuum, and encapsulated in Ga₄L₆^12- or Si₄L₆^8- assemblies within both a reaction field continuum solvent and in an aqueous molecular environment with counterions, to rationalize the rate enhancements observed experimentally for the reductive elimination reaction. We find that the Ga₄L₆^12- assembly lowers the energy barrier of the reaction compared to Si₄L₆^8-, which is consistent with kinetic trends observed experimentally. We have determined that the primary factor for catalytic rate acceleration stems from the electrostatic environment emanating from the Ga₄L₆^12- capsule as opposed to the water or counterions.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1532332

Journal Information:: Journal of Physical Chemistry Letters, Vol. 9, Issue 14; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 25 works

Citation information provided by
Web of Science

References (28)

Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen Jia, Hong-Peng; Quadrelli, Elsje Alessandra Chem. Soc. Rev., Vol. 43, Issue 2 https://doi.org/10.1039/C3CS60206K	journal	January 2014
Hydroxide complexes of the late transition metals: Organometallic chemistry and catalysis Nelson, David J.; Nolan, Steven P. Coordination Chemistry Reviews, Vol. 353 https://doi.org/10.1016/j.ccr.2017.10.012	journal	December 2017
A golden future in medicinal inorganic chemistry: the promise of anticancer gold organometallic compounds Bertrand, Benoît; Casini, Angela Dalton Trans., Vol. 43, Issue 11 https://doi.org/10.1039/C3DT52524D	journal	January 2014
Enantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C–C Bonds Cherney, Alan H.; Kadunce, Nathaniel T.; Reisman, Sarah E. Chemical Reviews, Vol. 115, Issue 17 https://doi.org/10.1021/acs.chemrev.5b00162	journal	July 2015
Transition-Metal-Catalyzed C–N Bond Forming Reactions Using Organic Azides as the Nitrogen Source: A Journey for the Mild and Versatile C–H Amination Shin, Kwangmin; Kim, Hyunwoo; Chang, Sukbok Accounts of Chemical Research, Vol. 48, Issue 4 https://doi.org/10.1021/acs.accounts.5b00020	journal	March 2015
Transition-metal catalysed C–N bond activation Wang, Quanjun; Su, Yijin; Li, Lixin Chemical Society Reviews, Vol. 45, Issue 5 https://doi.org/10.1039/C5CS00534E	journal	January 2016
Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination Arrechea, Pedro Luis; Buchwald, Stephen L. Journal of the American Chemical Society, Vol. 138, Issue 38 https://doi.org/10.1021/jacs.6b05990	journal	September 2016
Carbon–Carbon Bond-Forming Reductive Elimination from Isolated Nickel(III) Complexes Bour, James R.; Camasso, Nicole M.; Meucci, Elizabeth A. Journal of the American Chemical Society, Vol. 138, Issue 49 https://doi.org/10.1021/jacs.6b10350	journal	December 2016
Electronic Effects on Reductive Elimination To Form Carbon−Carbon and Carbon−Heteroatom Bonds from Palladium(II) Complexes Hartwig, John F. Inorganic Chemistry, Vol. 46, Issue 6 https://doi.org/10.1021/ic061926w	journal	March 2007
C−C Reductive Elimination in Palladium Complexes, and the Role of Coupling Additives. A DFT Study Supported by Experiment Pérez-Rodríguez, Martín; Braga, Ataualpa A. C.; Garcia-Melchor, Max Journal of the American Chemical Society, Vol. 131, Issue 10 https://doi.org/10.1021/ja808036j	journal	February 2009
Competition between sp ³ -C–N vs sp ³ -C–F Reductive Elimination from Pd ^IV Complexes Pérez-Temprano, Mónica H.; Racowski, Joy M.; Kampf, Jeff W. Journal of the American Chemical Society, Vol. 136, Issue 11 https://doi.org/10.1021/ja411433f	journal	February 2014
Experimental and Computational Assessment of Reactivity and Mechanism in C(sp ³ )–N Bond-Forming Reductive Elimination from Palladium(IV) Pendleton, Ian M.; Pérez-Temprano, Mónica H.; Sanford, Melanie S. Journal of the American Chemical Society, Vol. 138, Issue 18 https://doi.org/10.1021/jacs.6b02714	journal	April 2016
Exceptionally fast carbon–carbon bond reductive elimination from gold(III) Wolf, William J.; Winston, Matthew S.; Toste, F. Dean Nature Chemistry, Vol. 6, Issue 2 https://doi.org/10.1038/nchem.1822	journal	December 2013
Understanding the Mechanisms of Unusually Fast HH, CH, and CC Bond Reductive Eliminations from Gold(III) Complexes Nijamudheen, A.; Karmakar, Sharmistha; Datta, Ayan Chemistry - A European Journal, Vol. 20, Issue 45 https://doi.org/10.1002/chem.201403867	journal	September 2014
Electrophilic cleavage of organogold complexes with acids. The mechanism of the reductive elimination of dialkyl(aniono)gold(III) species Komiya, S.; Kochi, J. K. Journal of the American Chemical Society, Vol. 98, Issue 24 https://doi.org/10.1021/ja00440a025	journal	November 1976
A supramolecular microenvironment strategy for transition metal catalysis Kaphan, D. M.; Levin, M. D.; Bergman, R. G. Science, Vol. 350, Issue 6265 https://doi.org/10.1126/science.aad3087	journal	December 2015
Supermolecules by Design Caulder, Dana L.; Raymond, Kenneth N. Accounts of Chemical Research, Vol. 32, Issue 11 https://doi.org/10.1021/ar970224v	journal	November 1999
Computational optimization of electric fields for better catalysis design Welborn, Valerie Vaissier; Ruiz Pestana, Luis; Head-Gordon, Teresa Nature Catalysis, Vol. 1, Issue 9 https://doi.org/10.1038/s41929-018-0109-2	journal	September 2018
Scope and Mechanism of Cooperativity at the Intersection of Organometallic and Supramolecular Catalysis Levin, Mark D.; Kaphan, David M.; Hong, Cynthia M. Journal of the American Chemical Society, Vol. 138, Issue 30 https://doi.org/10.1021/jacs.6b05442	journal	July 2016
Electrostatic Origin of the Catalytic Effect of a Supramolecular Host Catalyst Frushicheva, Maria P.; Mukherjee, Shayantani; Warshel, Arieh The Journal of Physical Chemistry B, Vol. 116, Issue 45 https://doi.org/10.1021/jp3084327	journal	November 2012
Deconvoluting the Role of Charge in a Supramolecular Catalyst Hong, Cynthia M.; Morimoto, Mariko; Kapustin, Eugene A. Journal of the American Chemical Society, Vol. 140, Issue 21 https://doi.org/10.1021/jacs.8b01701	journal	May 2018
Mapping the genome of meta-generalized gradient approximation density functionals: The search for B97M-V Mardirossian, Narbe; Head-Gordon, Martin The Journal of Chemical Physics, Vol. 142, Issue 7 https://doi.org/10.1063/1.4907719	journal	February 2015
Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals Mardirossian, Narbe; Head-Gordon, Martin Molecular Physics, Vol. 115, Issue 19 https://doi.org/10.1080/00268976.2017.1333644	journal	April 2017
Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases VandeVondele, Joost; Hutter, Jürg The Journal of Chemical Physics, Vol. 127, Issue 11 https://doi.org/10.1063/1.2770708	journal	September 2007
cp2k: atomistic simulations of condensed matter systems Hutter, Jürg; Iannuzzi, Marcella; Schiffmann, Florian Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1 https://doi.org/10.1002/wcms.1159	journal	June 2013
Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi Computer Physics Communications, Vol. 167, Issue 2 https://doi.org/10.1016/j.cpc.2004.12.014	journal	April 2005
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny Molecular Physics, Vol. 113, Issue 2 https://doi.org/10.1080/00268976.2014.952696	journal	September 2014
Incorporating Solvation Effects into Density Functional Electronic Structure Calculations Chen, Jun L.; Noodleman, Louis; Case, David A. The Journal of Physical Chemistry, Vol. 98, Issue 43 https://doi.org/10.1021/j100094a013	journal	October 1994

Cited By (4)

Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold Welborn, Valerie Vaissier; Li, Wan-Lu; Head-Gordon, Teresa Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-019-14251-6	journal	January 2020
Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications Nijamudheen, A.; Datta, Ayan Chemistry – A European Journal, Vol. 26, Issue 7 https://doi.org/10.1002/chem.201903377	journal	December 2019
Electrostatic decoupling of periodic images of plane‐wave‐expanded densities and derived atomic point charges Blöchl, P. E. The Journal of Chemical Physics, Vol. 103, Issue 17 https://doi.org/10.1063/1.470314	journal	November 1995
Interplay of Water and a Supramolecular Capsule for Catalysis of Reductive Elimination Reaction from Gold Welborn, Valerie Vaissier; Li, Wan-Lu; Head-Gordon, Teresa arXiv https://doi.org/10.48550/arxiv.1908.10991	preprint	January 2019

Similar Records

Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold

Journal Article · Tue Jan 21 00:00:00 EST 2020 · Nature Communications · OSTI ID:1532332

Welborn, Valerie Vaissier; Li, Wan-Lu; Head-Gordon, Teresa

Catalytic Deprotection of Acetals In Strongly Basic Solution Usinga Self-Assembled Supramolecular 'Nanozyme'

Journal Article · Thu Jul 26 00:00:00 EDT 2007 · Angewandte Chemie International Edition · OSTI ID:1532332

Pluth, Michael D; Bergman, Robert G; Raymond, Kenneth N

Different and Often Opposing Forces Drive the Encapsulation and Multiple Exterior Binding of Charged Guests to a M ₄ L ₆ Supramolecular Vessel in Water

Journal Article · Wed Nov 08 00:00:00 EST 2017 · Chemistry - A European Journal · OSTI ID:1532332

Sgarlata, Carmelo; Mugridge, Jeffrey S.; Pluth, Michael D.; +3 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Electrostatics Generated by a Supramolecular Capsule Stabilizes the Transition State for Carbon–Carbon Reductive Elimination from Gold(III) Complex

Citation Formats

References (28)

Cited By (4)

Similar Records

Related Subjects