Oxidative Addition of Dihydrogen, Boron Compounds, and Aryl Halides to a Cobalt(I) Cation Supported by a Strong-Field Pincer Ligand
Cationic cobalt(I) dinitrogen complexes with a strong-field tridentate pincer ligand were prepared and the oxidative addition of polar and non-polar bonds was studied. Addition of H2 to [(iPrPNP)Co(N2)]+ (iPrPNP = 2,6-bis((diisopropylphosphaneyl)methyl)pyridine) in THF-d8 resulted in rapid oxidative...
| Veröffentlicht in: | Organometallics. - 1998. - 38(2019), 5 vom: 11. März, Seite 1081-1090 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2019
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| Zugriff auf das übergeordnete Werk: | Organometallics |
| Schlagworte: | Journal Article |
| Zusammenfassung: | Cationic cobalt(I) dinitrogen complexes with a strong-field tridentate pincer ligand were prepared and the oxidative addition of polar and non-polar bonds was studied. Addition of H2 to [(iPrPNP)Co(N2)]+ (iPrPNP = 2,6-bis((diisopropylphosphaneyl)methyl)pyridine) in THF-d8 resulted in rapid oxidative addition and formation of the cis-Co(III) dihydride complex, cis-[(iPrPNP)Co(H)2L]+ where L = THF or N2. The addition of H2 was reversible as evidenced by the dynamics observed by variable temperature 1H NMR spectroscopy and the regeneration of [(iPrPNP)Co(N2)]+ upon exposure to dinitrogen. In contrast, addition of HBPin, (Pin = pinacolato) B2Pin2 and aryl halides resulted in the formation of net one-electron oxidation products: cationic Co(II)-boryl and Co(II)-halide/aryl complexes, respectively. All products were structurally characterized by X-ray crystallography and the electronic structures were determined by a combination of magnetic moment measurements, EPR spectroscopy and DFT calculations. Monitoring the addition of HBPin to [(iPrPNP)Co(N2)]+ provided evidence for a transient Co(III) oxidative addition product that likely undergoes comproportionation with the cobalt(I) starting material to generate the observed Co(II) products |
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| Beschreibung: | Date Revised 28.09.2020 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 0276-7333 |
| DOI: | 10.1021/acs.organomet.8b00870 |