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Alkali Metal-Mediated Schlenk Dimerization of a Phosphorus-Substituted Alkene. Synthesis and Crystal Structures of Li, Na, and K Derivatives of a Phosphorus-Stabilized Butane-1,4-diide Ligand

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Department of Chemistry, School of Natural Sciences, Bedson Building, University of Newcastle, Newcastle upon Tyne, NE1 7RU, U.K.
Cite this: Organometallics 2003, 22, 18, 3684–3690
Publication Date (Web):July 31, 2003
https://doi.org/10.1021/om030393l
Copyright © 2003 American Chemical Society
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    Treatment of the vinylidene phosphine (Ph2P)2CCH2 (1) with either Li or Na in THF yields the bis(diphosphinomethanide) complexes {(THF)2Li(Ph2P)2CCH2}2 (2), {(pmdeta)2Li(Ph2P)2CCH2}2·(PhMe)3 (6), and [{(tmeda)1.5Na(Ph2P)2CCH2}2]n (3b), after recrystallization [tmeda = N,N,N‘,N‘-tetramethylethylenediamine, pmdeta = N,N,N‘,N‘‘,N‘‘-pentamethyldiethylenetriamine]. Treatment of 1 with K under the same conditions results in ligand degradation to give K(PPh2), which was isolated as the adduct {(pmdeta)K(PPh2)}n (4) after recrystallization from toluene/pmdeta, and unidentified organopotassium products. The potassium bis(diphosphinomethanide) [{(Ph2P)2CCH2CH2C(PPh2)2}2K4(pmdeta)(DME)3·(PhMe)2]n (5) may be accessed via a metathesis reaction between 2 and KO-t-Bu in ether, followed by recrystallization from toluene/DME in the presence of pmdeta [DME = 1,2-dimethoxyethane]. Compounds 3b, 4, 5, and 6 have been characterized by multielement NMR spectroscopy and X-ray crystallography.

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     Corresponding author. E-mail:  [email protected].

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    For 3b, 4, 5, and 6 details of structure determination, atomic coordinates, bond lengths and angles, and displacement parameters. This material is available free of charge via the Internet at http://pubs.acs.org. Observed and calculated structure factor details are available from the authors upon request.

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