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Sterically controlled mono- or dimetalation of a thioether-functionalized phosphine and an unusual light-induced phosphide-thiolate rearrangement

Lookup NU author(s): Dr Keith Izod, Dr Ross Harrington, Emeritus Professor Bill CleggORCiD


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The thioanisole-functionalized secondary phosphine {(Me3Si)2CH}PH(C6H4-2-SMe) (1) is readily accessible via the reaction of 2-LiC6H4SMe and {(Me3Si)2CH}PCl2, followed by reduction with LiAlH4. Compound 1 reacts with 1 equiv of n-BuLi in the presence of I equiv of tmeda in diethyl ether to give the lithium phosphide [{(Me3Si)2CH}P(C6H4-2-SMe)]Li-(tmeda ) (2) [tmeda = N,N,N,N-tetramethylethylenediamine]. In the absence of tmeda, compound I reacts with either 1 or 2 equiv of n-BuLi to give the phosphide-thiolate complex [{(Me3Si)2CH}P(C6H4-2-S)]{Li(OEt 2)}2 (4a), which may be recrystallized in the presence of tmeda as the adduct [{(Me3Si)2CH)P(C6H4-2-S)]{Li(tmeda)} 2 (4b). Compound 2 undergoes an unusual rearrangement on photolysis with white light to give the lithium thiolate [{(Me3Si)2CH)P(Me)(C6H4-2-S)]Li(tmed a) (6a), which may be recrystallized in the presence of 12-crown-4 as the adduct [{(Me3Si)2CH}P(Me)(C6H4-2-S)]Li(12-c rown-4) (6b). EPR experiments suggest that this rearrangement does not involve radical intermediates, but consists of a concerted migration of a methyl group from sulfur to phosphorus. Compounds 1, 2, 4a, 4b, 6a, and 6b have been characterized by multielement NMR spectroscopy; in addition, compounds 2, 4b, and 6b have been structurally characterized by X-ray crystallography.

Publication metadata

Author(s): Blair S, Izod K, Harrington RW, Clegg W

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 2003

Volume: 22

Issue: 2

Pages: 302-308

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: American Chemical Society


DOI: 10.1021/om0208265


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