Highly nucleophilic acetylide, vinyl, and vinylidene complexes. Final progress report, 1 January 1991--31 March 1994
In the course of this research the authors found that the anionic alkynyl complex [Cp{prime}(CO)(PPh{sub 3})Mn-C{triple_bond}C-CH{sub 3}]{sup {minus}} can be generated in situ by the addition of two equivalents of n-BuLi to a solution of the carbene complex Cp{prime}(CO)(PPh{sub 3})Mn{double_bond}C(OMe)CH{sub 2}CH{sub 3}. It was also found that the highly nucleophilic propynyl complex [Cp(CO)(PPh{sub 3})Mn-C{triple_bond}C-Me]{sup {minus}} reacts with a variety of aldehydes and ketones in the presence of BF{sub 3}{center_dot}Et{sub 2}O to give, after quenching with MeOH, a series of cationic vinylcarbyne complexes of the general form [Cp(CO)(PPh{sub 3})Mn{triple_bond}C-C(Me){double_bond}C(R)(R{prime})]BF{sub 4}. The cationic alkylidyne complexes [Cp(CO){sub 2}M{triple_bond}C-CH{sub 2}R]{sup +} [M = Re, R = H, M = Mn, R = H, Me, Ph] have been found to undergo facile deprotonation to give the corresponding neutral vinylidene complexes Cp(CO){sub 2}M{double_bond}C{double_bond}C(H)R. The authors have also investigated reactions relevant to the halide promoted Fe and Ru catalyzed carbonylation of nitroaromatics. The final part of this work has involved investigations of metal-oxo complexes.
- Research Organization:
- Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemistry
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG02-85ER13323
- OSTI ID:
- 10184990
- Report Number(s):
- DOE/ER/13323--T2; ON: DE95000404; BR: KC0302010
- Country of Publication:
- United States
- Language:
- English
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Generation of vinylcarbyne complexes from reaction of the propynyl complex [Cp(CO)(PPh[sub 3])MnC[triple bond]CMe][sup [minus]] with aldehydes and ketones
Addition, cycloaddition, and metathesis reactions of the cationic carbyne complexes [Cp(CO)[sub 2]Mn[triple bond]CCH[sub 2]R][sup +] and neutral vinylidene complexes Cp(CO)[sub 2]M=C=C(H)R (M = Mn, Re)