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Metal–Organic Frameworks Stabilize Mono(phosphine)–Metal Complexes for Broad-Scope Catalytic Reactions

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Department of Chemistry, University of Chicago, 929 East 57th Street, Chicago, Illinois 60637, United States
Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China
Cite this: J. Am. Chem. Soc. 2016, 138, 31, 9783–9786
Publication Date (Web):July 25, 2016
https://doi.org/10.1021/jacs.6b06239
Copyright © 2016 American Chemical Society

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    Abstract

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    Mono(phosphine)–M (M–PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal–organic framework (MOF) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C–H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M–PR3 intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.6b06239.

    • Crystallographic data for I·Rh (CIF)

    • Crystallographic data for I·Ir (CIF)

    • General experimental section; synthesis and characterization of ligands, and P1-MOF; crystal structure figure of I·Rh; details of the XAFS experiments, fitting method and model; procedures for MOF-catalyzed reactions (PDF)

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