Chakraborty, Uttam and Urban, Franziska and Muehldorft, Bernd and Rebreyend, Christophe and de Bruin, Bas and van Velzen, Niels and Harder, Sjoerd and Wolf, Robert (2016) Accessing the (CpNi)-Ni-Ar(I) Synthon: Reactions with N-Heterocyclic Carbenes, TEMPO, Sulfur, and Selenium. ORGANOMETALLICS, 35 (11). pp. 1624-1631. ISSN 0276-7333, 1520-6041
Full text not available from this repository. (Request a copy)Abstract
A reactive "(CpNiI)-Ni-Ar" surrogate (Cp-Ar = C-5(C6H4-4-Et)(5)) is accessible via the reduction of the dimer [(CpNi)-Ni-Ar(mu-Br)](2) with two equivalents of KC8. A trapping reaction with TEMPO afforded the new nickel(II) complex [(CpNi)-Ni-Ar(eta(2)-TEMPO)] (3), while the addition of N-heterocyclic carbenes gave the new nickel(I) radicals [(CpNi)-Ni-Ar(IPr)] (4a, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and [(CpNi)-Ni-Ar(IiPr(2)Me(2))] (4b, IiPr(2)Me(2) = 1,3-diisopropy1-4,5-dimethylimidazol-2-ylidene). EPR spectra supported by DFT calculations on 4a and 4b indicate that the spin density mainly resides at the nickel center. The reaction of the "(CpNi)-Ni-Ar(I) source" with yellow sulfur gave the Ni2S6 complex [((CpNi)-Ni-Ar)(2)(mu-S-6)] (5); the "subselenide" [((CpNi)-Ni-Ar)(2)(mu-Se-2)] (6) was formed in the analogous reaction with grey selenium. All new complexes were characterized by NMR, EPR, and UV-vis spectroscopy; their molecular structures were determined by X-ray crystallography.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | DENSITY-FUNCTIONAL CALCULATIONS; HYDROSULFIDO-BRIDGED DIIRIDIUM; ORDER REGULAR APPROXIMATION; METAL-ARENE INTERACTIONS; DIRHODIUM COMPLEXES; DIRUTHENIUM COMPLEX; MONOVALENT NICKEL; SULFIDO CLUSTERS; D(9) COMPLEXES; BOND-CLEAVAGE; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 18 Mar 2019 09:00 |
| Last Modified: | 18 Mar 2019 09:00 |
| URI: | https://pred.uni-regensburg.de/id/eprint/2773 |
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