Reactions of an amphoteric terminal tungsten methylidyne complex.
Treatment of [Tp'(CO)(2)W triple bond C--PPh(3)][PF(6)] (Tp' = hydridotris(3,5-dimethylpyrazolylborate)) with Na[HBEt(3)] in THF forms the methylidyne complex Tp'(CO)(2)W triple bond C--H via formyl and carbene intermediates Tp'(CO)(C(O)H)W triple bond C- PPh(3) and Tp'(CO)(2)W=C(PPh(3))(H), respectively. Spectroscopic features reported for Tp'(CO)(2)W triple bond C--H include the W triple bond C stretch (observed by both IR and Raman spectroscopy) and the (183)W NMR signal (detected by a (1)H, (183)W 2D HMQC experiment). Protonation of the Tp'(CO)(2)W triple bond C--H methylidyne complex with HBF(4).Et(2)O yields the cationic alpha-agostic methylidene complex [Tp'(CO)(2)W=CH(2)][BF(4)]. The methylidyne complex Tp'(CO)(2)W triple bond C-H can be deprotonated with alkyllithium reagents to provide the anionic terminal carbide Tp'(CO)(2)W triple bond C--Li; a downfield resonance at 556 ppm in the (13)C NMR spectrum has been assigned to the carbide carbon. The terminal carbide Tp'(CO)(2)W triple bond C-Li adds electrophiles at the carbide carbon to generate Tp'(CO)(2)W triple bond C--R (R = CH(3), SiMe(3), I, C(OH)Ph(2), CH(OH)Ph, and C(O)Ph) Fischer carbynes. A pK(a) of 28.7 was determined for Tp'(CO)(2)W triple bond C--H in THF by titrating the terminal carbide Tp'(CO)(2)W triple bond C--Li with 2-benzylpyridine and monitoring its conversion to Tp'(CO)(2)W triple bond C--H with in situ IR spectroscopy. Addition of excess Na[HBEt(3)] to neutral Tp'(CO)(2)W triple bond C--H generates the anionic methylidene complex [Na][Tp'(CO)(2)W=CH(2)]. The synthetic methodology for generating an anionic methylidene complex by hydride addition to neutral Tp'(CO)(2)W triple bond C--H contrasts with routes that utilize alpha-hydrogen abstraction or hydride removal from neutral methyl precursors to generate methylidene complexes. Addition of PhSSPh to the anionic methylidene complex in solution generates the saturated tungsten product Tp'(CO)(2)W(eta(2)-CH(2)SPh) by net addition of the SPh(+) moiety.
Enriquez
A E
AE
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.
White
P S
PS
Templeton
J L
JL