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Bulky β-Diketones Enabling New Lewis Acidic Ligand Platforms

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Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, United States
Cite this: Inorg. Chem. 2017, 56, 19, 11466–11469
Publication Date (Web):September 21, 2017
https://doi.org/10.1021/acs.inorgchem.7b02077
Copyright © 2017 American Chemical Society

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    Abstract

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    The synthesis of a sterically encumbered β-diketone ligand (Aracac) substituted with 2,6-(2,4,6-Me3C6H2)2C6H3 is described. Coordination complexes of the type M(Aracac)2Cl(solv) (M = Ti, V, Cr; solv = THF, CH3CN) were prepared by the reaction of Aracac with MCl3 (M = V, Cr) or with TiCl4 to generate Ti(Aracac)2Cl2, followed by reduction. These complexes show a trend of alternating the cis/trans geometric preference with increasing dn electron count (n = 0, 1, 2, 3), which is rationalized in part by the unusual ability of β-diketonates to behave as either a weak π donor or a π acceptor in the cis and trans geometries, respectively. In this way, the bis-β-diketonate platform can accommodate the varying electronic demands of the coordinated metal ion. These results demonstrate the ability to limit the coordination of β-diketonates on metal complexes for the first time, providing a chemically robust and coordinatively versatile platform for mechanistic investigations, metal functionalization, and improved catalyst design.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b02077.

    • Experimental procedures, NMR data, EPR data, UV–vis spectra, IR spectra, mass spectrometry data, computational data, crystallographic details, and tables (PDF)

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    CCDC 15563981556400 and 15627641562765 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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