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Ligand Design for Isomer-Selective Oxorhenium(V) Complex Synthesis
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    Ligand Design for Isomer-Selective Oxorhenium(V) Complex Synthesis
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    Department of Chemical and Environmental Engineering, University of California, Riverside, California 92521, United States
    Department of Civil and Environmental Engineering, Colorado School of Mines, Golden, Colorado 80401, United States
    § Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230000, China
    Department of Civil and Environmental Engineering and Department of Chemistry, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States
    # Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States
    Δ Department of Civil, Architectural, and Environmental Engineering, University of Texas at Austin, Austin, Texas 78712, United States
    *E-mail: [email protected]. (J.L.)
    *E-mail: [email protected]. (T.J.S.)
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2017, 56, 3, 1757–1769
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    https://doi.org/10.1021/acs.inorgchem.6b03076
    Published January 12, 2017
    Copyright © 2017 American Chemical Society

    Abstract

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    Recently, N,N-trans Re(O)(LN–O)2X (LN–O = monoanionic N–O chelates; X = Cl or Br prior to being replaced by solvents or alkoxides) complexes have been found to be superior to the corresponding N,N-cis isomers in the catalytic reduction of perchlorate via oxygen atom transfer. However, reported methods for Re(O)(LN–O)2X synthesis often yield only the N,N-cis complex or a mixture of trans and cis isomers. This study reports a geometry-inspired ligand design rationale that selectively yields N,N-trans Re(O)(LN–O)2Cl complexes. Analysis of the crystal structures revealed that the dihedral angles (DAs) between the two LN–O ligands of N,N-cis Re(O)(LN–O)2Cl complexes are less than 90°, whereas the DAs in most N,N-trans complexes are greater than 90°. Variably sized alkyl groups (−Me, −CH2Ph, and −CH2Cy) were then introduced to the 2-(2′-hydroxyphenyl)-2-oxazoline (Hhoz) ligand to increase steric hindrance in the N,N-cis structure, and it was found that substituents as small as −Me completely eliminate the formation of N,N-cis isomers. The generality of the relationship between N,N-trans/cis isomerism and DAs is further established from a literature survey of 56 crystal structures of Re(O)(LN–O)2X, Re(O)(LO–N–N–O)X, and Tc(O)(LN–O)2X congeners. Density functional theory calculations support the general strategy of introducing ligand steric hindrance to favor synthesis of N,N-trans Re(O)(LN–O)2X and Tc(O)(LN–O)2X complexes. This study demonstrates the promise of applying rational ligand design for isomeric control of metal complex structures, providing a path forward for innovations in a number of catalytic, environmental, and biomedical applications.

    Copyright © 2017 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b03076.

    • NMR spectra, tabulated dihedral angles, additional references (PDF)

    • Calculated structure coordinate file (XYZ)

    • Crystallographic data (CIF)

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    This article is cited by 13 publications.

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2017, 56, 3, 1757–1769
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.6b03076
    Published January 12, 2017
    Copyright © 2017 American Chemical Society

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