Pelties, Stefan and Maier, Thomas and Herrmann, Dirk and de Bruin, Bas and Rebreyend, Christophe and Gaertner, Stefanie and Shenderovich, Ilya G. and Wolf, Robert (2017) Selective P-4 Activation by a Highly Reduced Cobaltate: Synthesis of Dicobalt Tetraphosphido Complexes. [["eprint_typename_proceedings" not defined]]
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Although the chemistry of transition metal polyphosphide anions has attracted significant attention, there are few reports of studies in which such species have been synthesized directly from white phosphorus. [K(OEt2)(2){Co(BIAN)(cod)}] (1, BIAN=1,2-bis(2,6-diisopropylphenylimino)acenaphthene, cod=1,5-cyclooctadiene), which is readily prepared by ligand exchange from [K(thf)(x){Co(cod)(2)}], reacts with P-4 to afford [{K(thf)}(2){(BIAN)Co}(2)(-(4):(4)-P-4)] (2a) in 61% yield (isolated product). [{K(OEt2)}(2){(BIAN)Co}(2)(-(4):(4)-P-4)] (2b) and [K([18]crown-6)(MeCN)](2)[{(BIAN)Co}(2)(-(4):(4)-P-4)] (2c) were obtained by recrystallizing 2a from diethyl ether and acetonitrile (and using [18]crown-6 in case of 2c). Oxidation of 2a with [Cp2Fe]BAr4F (one equivalent) and subsequent recrystallization of the product from different solvents gave [K(OEt2){(BIAN)Co}(2)(-(4):(4)-P-4)] (3a) and [K(dme)(4)][{(BIAN)Co}(2)(-(4):(4)-P-4)] (3b; dme=1,2-dimethoxyethane). Neutral [{(BIAN)Co}(2)(-(4):(4)-P-4)] (4) was obtained in moderate yield by oxidizing 2a with two equivalents of [Cp2Fe]BAr4F. The new complexes were characterized by NMR, EPR (in the case of 3a), and UV/Vis spectroscopy, and elemental analysis. The molecular structures revealed by X-ray crystallography display planar cyclic or open-chain P-4(4-) units sandwiched between {(BIAN)Co} fragments.
| Item Type: | ["eprint_typename_proceedings" not defined] |
|---|---|
| Uncontrolled Keywords: | TRANSITION-METAL-COMPLEXES; DIIMINE-DITHIOLATE COMPLEXES; P BOND FORMATION; WHITE PHOSPHORUS; MOLECULAR-STRUCTURE; STRUCTURAL-CHARACTERIZATION; COPPER(II) COMPLEXES; CALCIUM COMPLEXES; CHARGE-TRANSFER; LIGANDS; anions; cobalt; phosphorus; polyphosphides; redox-active ligands |
| 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: | 14 Dec 2018 13:10 |
| Last Modified: | 11 Feb 2019 13:45 |
| URI: | https://pred.uni-regensburg.de/id/eprint/900 |
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