Spectroscopic, Magnetic, and Computational Investigations on a Series of Rhenium(III) Cyclopentadienide β-diketiminate Halide and Pseudohalide Complexes
| Autor: | Robert G. Bergman, John Arnold, Laurent Maron, Daniel J. Lussier, Khetpakorn Chakarawet, Jorge Ivan Amaro Estrada, Trevor D. Lohrey, Erik T. Ouellette |
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| Přispěvatelé: | University of California (UC), Lawrence Berkeley National Laboratory [Berkeley] (LBNL), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2022 |
| Předmět: |
MAIN-GROUP ELEMENTS
Series (mathematics) LAT ISOMERIZATION TRANSITION-METALS Organic Chemistry MULTIPLE BONDS chemistry.chemical_element Halide Rhenium DFT CALCULATIONS REACTIVITY Inorganic Chemistry β diketiminate SOLID-STATE X-RAY STRUCTURES chemistry RESONANCE SPECTRA Polymer chemistry [CHIM]Chemical Sciences CRYSTAL-STRUCTURE Physical and Theoretical Chemistry |
| Zdroj: | Organometallics Organometallics, 2022, 41 (22), pp.3128-3137. ⟨10.1021/acs.organomet.1c00516⟩ |
| ISSN: | 0276-7333 1520-6041 |
| Popis: | International audience; The low-valent rhenium(I) salt Na[Re(η5-Cp)(BDI)] (BDI = N,N′-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) was shown to react with various halide and chalcogenolate reagents, leading to the isolation of a series of rhenium(III)–halide and −pseudohalide complexes: Re(X)(η5-Cp)(BDI) (1-X, X = F, Cl, Br, I; 2, X = OTf) and Re(ER)(η5-Cp)(BDI) (3-ER, ER = SBn, SeBn, TePh). The 1H NMR spectra of these complexes displayed sharp resonances shifted several ppm from typical diamagnetic regions, as well as distinct chemical shift trends down both the halide (with the exception of F) and chalcogenolate series, with both Cp and BDI backbone peaks moving downfield with increasing atomic number. Subsequent magnetic susceptibility measurements of the rhenium(III) halides 1-Cl, 1-Br, and 1-I indicated that these complexes display temperature-independent paramagnetism (TIP), with χTIP values of 7.41(44) × 10–4 to 1.50(51) × 10–3 cm3 mol–1. Multireference complete active space self-consistent field (CASSCF) computations incorporating spin–orbit state mixing revealed small energy separations (1.7–3.0 kcal/mol) between thermally isolated ground states and the first excited spin–orbit states for the rhenium halides, confirming that low-lying excited states are responsible for the observed TIP behavior. |
| Databáze: | OpenAIRE |
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