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Unusual solvent-promoted smiles rearrangement of two different phosphorus-containing organolithium compounds to the same lithium phosphide. Crystal structure of MeP{C6H4-2-CH(C6H4-2-CH2N Me2)NMe2}Li(THF)2

Lookup NU author(s): Dr Keith Izod, Paul O'Shaughnessy, Emeritus Professor Bill CleggORCiD


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Treatment of the tertiary phosphines RP(C6H4-2-CH2NMe2)2 (R = Me, 1; R = i-Pr, 4) with n-BuLi in THF yields the lithium phosphides [RP{C6H4-2-CH(C6H4-2-CH2N Me2)NMe2}]Li-(THF)2 (R = Me, 5; R = i-Pr, 6) as the sole phosphorus-containing products. Compound 5 is also obtained when either the lithium phosphinomethanide Li{CH2P(C6H4-2-CH2NMe2) 2} (3) or the benzyllithium complex [MeP(C6H4-2-CH2NMe2){C6H 4-2-CH(Li)NMe2}]2 (2) is dissolved in THF. Conversion of 2 to 5 is extremely rapid, whereas conversion of 3 to 5 takes several days at room temperature. The deuterium-labeled compound Li{CH2P(C6H4-2-CD2NMe2) 2} (3a) isomerizes in THF to DCH2P(C6H4-2-CD(C6H4-2-CD 2NMe2)NMe2}Li-(THF)2 (5a) and shows a strong kinetic isotope effect in comparison to the isomerization of 3. Compounds 5 and 6 have been characterized by multinuclear NMR spectroscopy and X-ray crystallography, and a mechanism for their formation from 1-4 is proposed.

Publication metadata

Author(s): Izod K; Clegg W; O'Shaughnessy P

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 2002

Volume: 21

Issue: 4

Pages: 641-646

ISSN (print): 0276-7333

ISSN (electronic):

Publisher: American Chemical Society


DOI: 10.1021/om010856s


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