期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 23, 期 25, 页码 6094-6102出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201603296
关键词
anions; cobalt; phosphorus; polyphosphides; redox-active ligands
资金
- Deutsche Forschungsgemeinschaft
- Netherlands Organization for Scientific Research (NWO-CW VICI project) [016.122.613]
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.
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