NNN-Cobalt(II) pincer complexes: paramagnetic NMR spectroscopy in solution and application as hydrosilylation catalysts
The tridentate, monoanionic bis(oxazolinylmethylidene)-isoindolate pincer ligand was utilized for the synthesis of various cobalt(II)high-spincomplexes. Employing standard complexation procedures, the corresponding acetato and chlorido complexes were isolated in good yields and thoroughly characteri...
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| Hauptverfasser: | , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
20 May 2020
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| In: |
European journal of inorganic chemistry
Year: 2020, Heft: 24, Pages: 2335-2342 |
| ISSN: | 1099-0682 |
| DOI: | 10.1002/ejic.202000378 |
| Online-Zugang: | Verlag, kostenfrei, Volltext: https://doi.org/10.1002/ejic.202000378
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| Verfasserangaben: | Clemens K. Blasius, Hubert Wadepohl, and Lutz H. Gade |
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| 520 | |a The tridentate, monoanionic bis(oxazolinylmethylidene)-isoindolate pincer ligand was utilized for the synthesis of various cobalt(II)high-spincomplexes. Employing standard complexation procedures, the corresponding acetato and chlorido complexes were isolated in good yields and thoroughly characterized in the solid-state and in solution. In particular, a density functional theory (DFT) supported paramagnetic NMR analysis revealed a strong correlation between observed(13)C NMR shifts and calculated spin-density distributions, allowing for an unambiguous signal assignment in all(1)H and(13)C NMR spectra. An acetato-bridged trinuclear cobalt species as well as the hexacoordinate "homoleptic" complex [((R)boxmi)(2)Co] were further identified as side products generated in the complex synthesis. The chlorido complexes were applied as catalysts for the cobalt-catalyzed hydrosilylation of acetophenone, producing the chiral secondary alcohol with moderate enantioselectivities. | ||
| 650 | 4 | |a 3D metal complexes | |
| 650 | 4 | |a alkyl complexes | |
| 650 | 4 | |a basis-sets | |
| 650 | 4 | |a bis(oxazoline) ligands | |
| 650 | 4 | |a Cobalt | |
| 650 | 4 | |a cobalt complexes | |
| 650 | 4 | |a enantioselective hydroboration | |
| 650 | 4 | |a Hydrosilylation | |
| 650 | 4 | |a markovnikov hydrosilylation | |
| 650 | 4 | |a metal | |
| 650 | 4 | |a molecular-orbital methods | |
| 650 | 4 | |a Paramagnetic NMR | |
| 650 | 4 | |a Pincer ligands | |
| 650 | 4 | |a reaction pathways | |
| 650 | 4 | |a zeta valence quality | |
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