Bueschelberger, Philipp and Gaertner, Dominik and Reyes-Rodriguez, Efrain and Kreyenschmidt, Friedrich and Koszinowski, Konrad and Jacobi von Wangelin, Axel and Wolf, Robert (2017) Alkene Metalates as Hydrogenation Catalysts. CHEMISTRY-A EUROPEAN JOURNAL, 23 (13). pp. 3139-3151. ISSN 0947-6539, 1521-3765
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First-row transition-metal complexes hold great potential as catalysts for hydrogenations and related reductive reactions. Homo-and heteroleptic arene/alkene metalates(1-) (M=Co, Fe) are a structurally distinct catalyst class with good activities in hydrogenations of alkenes and alkynes. The first syntheses of the heteroleptic cobaltates [K([18]crown-6)][Co(eta(4)-cod)(eta(2)-styrene)(2)] (5) and [K([18]crown-6)][Co(eta(4)-dct)(eta(4)-cod)] (6), and the homoleptic complex [K(thf)(2)][Co(eta(4)-dct)(2)] (7; dct=dibenzo[a,e]cyclooctatetraene, cod=1,5-cyclooctadiene), are reported. For comparison, two cyclopentadienylferrates(1-) were synthesized according to literature procedures. The isolated and fully characterized monoanionic complexes were competent precatalysts in alkene hydrogenations under mild conditions (2 bar H-2, r. t., THF). Mechanistic studies by NMR spectroscopy, ESI mass spectrometry, and poisoning experiments documented the operation of a homogeneous mechanism, which was initiated by facile redox-neutral pi-ligand exchange with the substrates followed by H-2 activation. The substrate scope of the investigated precatalysts was also extended to polar substrates (ketones and imines).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | OLEFIN HYDROGENATION; TRANSITION-METALS; COBALT COMPLEXES; IRON CATALYSTS; HOMOGENEOUS HYDROGENATION; ASYMMETRIC HYDROGENATION; SELECTIVE HYDROGENATION; COUPLING REACTIONS; DIALKYL COMPLEXES; MASS-SPECTROMETRY; cobalt; hydrogenation; iron; reaction mechanisms; transition metals |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 14 Dec 2018 13:00 |
| Last Modified: | 11 Feb 2019 10:36 |
| URI: | https://pred.uni-regensburg.de/id/eprint/264 |
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