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Title: Scope and Mechanism of Cooperativity at the Intersection of Organometallic and Supramolecular Catalysis

Abstract

Here, the scope and mechanism of the microenvironment-catalyzed C(sp3)-C(sp3) reductive elimination from transition metal complexes [Au(III), Pt(IV)] is explored. Experiments detailing the effect of structural perturbation of neutral and anionic spectator ligands, reactive alkyl ligands, solvent, and catalyst structure are disclosed. Indirect evidence for a coordinatively unsaturated encapsulated cationic intermediate is garnered via observation of several inactive donor-arrested inclusion complexes, including a crystallographically characterized encapsulated Au(III) cation. Finally, based on stoichiometric experiments under catalytically relevant conditions, a detailed mechanism is outlined for the dual supramolecular and platinum-catalyzed C-C coupling between methyl iodide and tetramethyltin. Determination of major platinum species present under catalytic conditions and subsequent investigation of their chemistry reveals an unexpected interplay between cis-trans isomerism and the supramolecular catalyst in a Pt(II)/Pt(IV) cycle, as well as several off-cycle reactions.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Institutes of Health (NIH); National Science Foundation (NSF)
OSTI Identifier:
1464140
Grant/Contract Number:  
AC02-05CH11231; R01 GM073932; DGE 1106400
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 30; Related Information: © 2016 American Chemical Society.; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Levin, Mark D., Kaphan, David M., Hong, Cynthia M., Bergman, Robert G., Raymond, Kenneth N., and Toste, F. Dean. Scope and Mechanism of Cooperativity at the Intersection of Organometallic and Supramolecular Catalysis. United States: N. p., 2016. Web. doi:10.1021/jacs.6b05442.
Levin, Mark D., Kaphan, David M., Hong, Cynthia M., Bergman, Robert G., Raymond, Kenneth N., & Toste, F. Dean. Scope and Mechanism of Cooperativity at the Intersection of Organometallic and Supramolecular Catalysis. United States. doi:https://doi.org/10.1021/jacs.6b05442
Levin, Mark D., Kaphan, David M., Hong, Cynthia M., Bergman, Robert G., Raymond, Kenneth N., and Toste, F. Dean. Tue . "Scope and Mechanism of Cooperativity at the Intersection of Organometallic and Supramolecular Catalysis". United States. doi:https://doi.org/10.1021/jacs.6b05442. https://www.osti.gov/servlets/purl/1464140.
@article{osti_1464140,
title = {Scope and Mechanism of Cooperativity at the Intersection of Organometallic and Supramolecular Catalysis},
author = {Levin, Mark D. and Kaphan, David M. and Hong, Cynthia M. and Bergman, Robert G. and Raymond, Kenneth N. and Toste, F. Dean},
abstractNote = {Here, the scope and mechanism of the microenvironment-catalyzed C(sp3)-C(sp3) reductive elimination from transition metal complexes [Au(III), Pt(IV)] is explored. Experiments detailing the effect of structural perturbation of neutral and anionic spectator ligands, reactive alkyl ligands, solvent, and catalyst structure are disclosed. Indirect evidence for a coordinatively unsaturated encapsulated cationic intermediate is garnered via observation of several inactive donor-arrested inclusion complexes, including a crystallographically characterized encapsulated Au(III) cation. Finally, based on stoichiometric experiments under catalytically relevant conditions, a detailed mechanism is outlined for the dual supramolecular and platinum-catalyzed C-C coupling between methyl iodide and tetramethyltin. Determination of major platinum species present under catalytic conditions and subsequent investigation of their chemistry reveals an unexpected interplay between cis-trans isomerism and the supramolecular catalyst in a Pt(II)/Pt(IV) cycle, as well as several off-cycle reactions.},
doi = {10.1021/jacs.6b05442},
journal = {Journal of the American Chemical Society},
number = 30,
volume = 138,
place = {United States},
year = {2016},
month = {7}
}

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Cited by: 30 works
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Figures / Tables:

Figure 1 Figure 1: A supramolecular approach for transition metal catalyzed cross-coupling.

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