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X-ray structure and electrophilic reactivity of a cationic, chiral tungsten(II) methylene complex by Aase S. Jepsen; Neil J. Vogeley; Peter S. White; Joseph L. Templeton is a Chemistry article available to read on EtoBox.

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The structure of a tungsten(II) methylene complex, [Tp%(CO)(PhCCMe)W CH 2 ][BAr% 4 ] (2a), was obtained by taking advantage of the stabilizing, weakly coordinating counterion, BAr 4 ́-, to form X-ray quality single crystals. The electrophilic reactivity of [Tp%(CO)(PhCCMe)W CH 2 ][PF 6 ] (2b) was surveyed with both neutral nucleophiles (triphenylphosphine and pyridine) and anionic nucleophiles (formed by deprotonation of phthalimide, diethyl malonate, t-butyl acetoacetate, and acetophenone) to give derivatives of the form [Tp%(CO)(PhCCMe)W CH 2 Nu] + ,0 . Crystal structures obtained for the phthalimide (5) and diethyl malonate (6) adducts are compatible with attack of the nucleophile from along the metal CO axis. The stereochemistry of the t-butyl acetoacetate adduct was determined by 2-D NOESY-NMR. Reaction of methylene carbene 2b with cyclohexene sulfide results in sulfur atom transfer to form a rare p-bound thioformaldehyde complex (9).

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Author

Aase S. Jepsen; Neil J. Vogeley; Peter S. White; Joseph L. Templeton

Publisher

Elsevier Science; Elsevier ; Elsevier BV (ISSN 0022-328X)

Published

2001

Language

EN

Field

Chemistry (Physical Sciences)