Reductive coupling of carbon monoxide to C sub 2 products
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; USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG05-85ER13430
- OSTI ID:
- 5764454
- Report Number(s):
- DOE/ER/13430-T1; ON: DE92007529
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBON 13
NUCLEAR MAGNETIC RESONANCE
TUNGSTEN COMPLEXES
CHEMICAL PREPARATION
CARBYNES
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PROGRESS REPORT
CARBON
CARBON ISOTOPES
COMPLEXES
DOCUMENT TYPES
ELEMENTS
EVEN-ODD NUCLEI
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NONMETALS
NUCLEI
ORGANIC COMPOUNDS
RADICALS
RESONANCE
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties