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: Blasius, Clemens K. (VerfasserIn) , Wadepohl, Hubert (VerfasserIn) , Gade, Lutz H. (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 20 May 2020
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
Beschreibung
Zusammenfassung: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.
Beschreibung:Gesehen am 27.07.2020
Beschreibung:Online Resource
ISSN:1099-0682
DOI:10.1002/ejic.202000378