Ziegler, Christoph G. P. and Maier, Thomas M. and Pelties, Stefan and Taube, Clemens and Hennersdorf, Felix and Ehlers, Andreas W. and Weigand, Jan J. and Wolf, Robert (2019) Construction of alkyl-substituted pentaphosphido ligands in the coordination sphere of cobalt. CHEMICAL SCIENCE, 10 (5). pp. 1302-1308. ISSN 2041-6520, 2041-6539
Full text not available from this repository. (Request a copy)Abstract
Rare mono-and diorganopentaphosphido cobalt complexes are accessible by P-P condensation using the unprecedented, reactive cobalt-gallium tetraphosphido complex [K(dme)(2){((Mes)BIAN) Co(mu-eta(4):eta(2)-P-4) Ga(nacnac)}] (2). Compound 2 was prepared in good yield by reaction of [K(Et2O){(MesBIAN) Co(h 4-1,5cod)}] [1, BIAN = bis(mesitylimino) acenaphthene diimine, cod = 1,5-cyclooctadiene] with [Ga(nacnac)(eta(2)-P4)] (nacnac = CH[CMeN(2,6-iPr(2)C(6)H(3))](2)). Reactions with R2PCl (R = iPr, tBu, and Cy) selectively afford [((Mes)BIAN)Co(cyclo-P5R2)] (3a-c), which feature eta(4)-coordinated 1,1-diorganopentaphosphido ligands. The mechanism of formation of these species has been studied by P-31{H-1} NMR spectroscopy and DFT calculations. In the case of 3a (R = iPr), it was possible to identify the intermediate [((Mes)BIAN)Co(mu-eta(4):eta(2)-P(5)iPr(2)) Ga(nacnac)] (4) by single-crystal X-ray diffraction. A related, monosubstituted organopentaphosphido cobalt complex [((Mes)BIAN)Co(mu-eta(4):eta(1)-P(5)tBu) GaCl(nacnac)] (5) was isolated by reacting dichloroalkylphosphane tBuPCl(2) with 2. Heterobimetallic complexes such as 2 thus may enable the targeted construction of a range of new metal-coordinated polyphosphorus frameworks by P-P condensation.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | P-P BOND; WHITE PHOSPHORUS; P-4 ACTIVATION; FUNCTIONALIZATION; COMPLEX; TRANSFORMATION; HYDROLYSIS; REACTIVITY; CHEMISTRY; PHOSPHIDE; |
| 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: | 22 Apr 2020 04:56 |
| Last Modified: | 22 Apr 2020 04:56 |
| URI: | https://pred.uni-regensburg.de/id/eprint/27561 |
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