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Open Access Alkali Metal Phenylphosphandiides, [M2PnPhn] (M = Li, Na)

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The reaction of phenyldichlorophosphane, PhPCl2, a commercially important precursor for organophosphorus compounds, with lithium and sodium as reducing metals was re-investigated with the aim to well-characterize the resulting oligophosphandiides, [M2(PnPhn)(solv)x] (M = Li, Na). Experimental conditions for the optimal formation of these compounds were found for both series with M = Li and M = Na and several of these were crystallized and characterized by X-ray diffraction studies. As a result, we find that sodium strongly prefers ion triple structures [M2(PnPhn)(solv)x] over solvent-separated ion pairs, [M(solv)m]+[MPnPhn(solv)n], which have a higher tendency to form with M = Li. Also, while [Na2(P4Ph4)(solv)x] retains its structure in thf solution, [Li2(P4Ph4)(solv)x] partially dissociates into the radical anion (Ph2P2).− which is detected by EPR spectroscopy. The knowledge about the structures and the behavior of the alkali metal diphosphandiides allows us to propose a reaction mechanism for their formation.

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Keywords: ALKALI METALS; ION TRIPLES; PHOSPHANES; PHOSPHORUS; RADICALS

Document Type: Research Article

Publication date: March 1, 2005

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  • International Journal for Chemistry and Official Membership Journal of the Swiss Chemical Society (SCS) and its Divisions

    CHIMIA, a scientific journal for chemistry in the broadest sense, is published 10 times a year and covers the interests of a wide and diverse readership. Contributions from all fields of chemistry and related areas are considered for publication in the form of Review Articles and Notes. A characteristic feature of CHIMIA are the thematic issues, each devoted to an area of great current significance.

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