A family of tri- and dimetallic pyridine dicarboxamide cryptates: unusual O,N,O-coordination and facile access to secondary coordination sphere hydrogen bonding interactions
| Autor: | Ricardo Garcia-Serres, Erik Čižmár, Matthew W. Calkins, Gary L. Guillet, Gianna N. Di Francesco, Khalil A. Abboud, Mark W. Meisel, Leslie J. Murray, Jesse B. Gordon |
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| Přispěvatelé: | Department of Chemistry, University of Florida, University of Florida [Gainesville] (UF), National High Magnetic Field Laboratory, P.J. Safarik University, Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire de Physico-chimie des Métaux en Biologie (LPCMB), Université Joseph Fourier - Grenoble 1 (UJF)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Joseph Fourier - Grenoble 1 (UJF) |
| Rok vydání: | 2015 |
| Předmět: |
Models
Molecular Coordination sphere Stereochemistry Pyridines Molecular Conformation chemistry.chemical_element Protonation [CHIM.INOR]Chemical Sciences/Inorganic chemistry 010402 general chemistry 01 natural sciences Inorganic Chemistry Metal chemistry.chemical_compound Amide Pyridine Hydroxides Organometallic Compounds [CHIM.COOR]Chemical Sciences/Coordination chemistry Physical and Theoretical Chemistry Trigonal planar molecular geometry 010405 organic chemistry Hydrogen bond Hydrogen Bonding Oxides Amides 0104 chemical sciences Nickel Crystallography chemistry visual_art visual_art.visual_art_medium |
| Zdroj: | Inorganic Chemistry Inorganic Chemistry, 2015, 54 (6), pp.2691-2704. ⟨10.1021/ic502873d⟩ Inorganic Chemistry, American Chemical Society, 2015, 54 (6), pp.2691-2704. ⟨10.1021/ic502873d⟩ |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic502873d⟩ |
| Popis: | International audience; A series of tri- and dimetallic metal complexes of pyridine dicarboxamide cryptates are reported in which changes to the base and metal source result in diverse structure types. Addition of strong bases, such as KH or KN(SiMe3)2, followed by divalent metal halides allows direct access to trinuclear complexes in which each metal center is coordinated by a dianionic N,N,N-chelate of each arm. These complexes bind a guest K+ cation within the central cavity in a trigonal planar coordination environment. Minor changes to the solvent and equivalents of base used in the syntheses of the triiron(II) and tricobalt(II) complexes affords two trinuclear clusters with atypical O,N,O-coordination by each pyridine dicarboxamide arm; the amide carbonyl O atoms are oriented toward the interior of the cavity to coordinate to each metal center. Finally, varying the base enables the selective synthesis of dinuclear nickel(II) and copper(II) complexes in which one pyridine dicarboxamide arm remains protonated. These amide protons are at one end of a hydrogen bonding network that extends throughout the internal cavity and terminates at a metal bound hydroxide, carbonate, or bicarbonate donor. In the dinickel complex, the bicarbonate cannot be liberated as CO2 either thermally or upon sparging with N2, which differs from previously reported monometallic complexes. The carbonate or bicarbonate ligands likely arise from sequestration of atmospheric CO2 based on the observed reaction of the di(hydroxonickel) analog. |
| Databáze: | OpenAIRE |
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