Reductive coupling of carbon monoxide to C{sub 2} products. Progress report, May 1990--November 1991
We first prepared Tp{prime}(CO){sub 2}W{equivalent_to}CH from a conversion of the cationic phosphonium carbyne Tp{prime}(CO){sub 2}W{equivalent_to}CPMe{sub 3}+ to a neutral carbene by hydride addition at carbon. Removal of PMe{sub 3} with a Lewis acid trap yielded milligram quantities of the desired terminal carbyne. More recently we have prepared a silylcarbyne precursor which reacts with Bu{sub 4}NF in wet THF to form substantial amounts of the CH carbyne. Dimerization to form an unusual vinylidene bridged complex is a facile decomposition route which consumes the Tp{prime}(CO){sub 2}M{equivalent_to}CH monometer for both M=MO and M=W,. Preparation of other carbyne complexes has been achieved using Tp{prime}(CO){sub 2}W{equivalent_to}C-Cl as a reagent. Another carbyne derivative was synthesized from Tp{prime}(CO){sub 2}M{equivalent_to}C-Cl by adding K[CpFe(Co){sub 2}] to displace the chloride. Organometallic products formed from the reaction of an electrophilic iron carbene complex with nitrosoarenes or azobenzene reflect net insertion of the ArN-X moiety into the Fe=CHAr bond. Cp(CO){sub 2}Fe-O-N(Ar{prime})=CHAr+ and Cp(CO){sub 2}FeN(Ph)-N(Pha)=CHAr+ have been isolated and spectroscopically characterized. More promising results for long term progress in building electrophilic nitrene complexes have been achieved with Group VI reagents. Simple methods for generating Tp{prime}(CO){sub 2}W=NHR for R= Ar and Bu{sup t} are encouraging. Furthermore, removal of H{sup minus} from the amido ligand with either I{sub 2} or [Ph{sub 3}C][BF{sub 4}] provides access to cationic nitrene complexes.
- Research Organization:
- North Carolina Univ., Chapel Hill, NC (United States). Dept. of Chemistry
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG05-85ER13430
- OSTI ID:
- 10120995
- Report Number(s):
- DOE/ER/13430-T1; ON: DE92007529
- Resource Relation:
- Other Information: PBD: Aug 1991
- Country of Publication:
- United States
- Language:
- English
Similar Records
Reactions of (Cp(CO) sub 2 Fe double bond CHAr) sup + (Ar = p-C sub 6 H sub 4 OMe) with O double bond N-Ar prime (Ar prime = C sub 6 H sub 5 , p-C sub 6 H sub 4 NMe sub 2 ) and PhN double bond NPh
Bond forming reactions of carbyne and nitrene complexes. Final technical report for DE-FG02-96ER14608