131863-71-3Relevant academic research and scientific papers
Addition of Inorganic and Organic Nucleophiles to the Vinylidene Ligand of the Cluster FeCo2(CO)9(μ3-C=CH2)
Albiez, Thomas,Heineke, Daniel,Vahrenkamp, Heinrich
, p. 1025 - 1034 (2007/10/02)
The C=CH2 ligand of the cluster FeCo2(CO)9(μ3-C=CH2) (1) is electrophilic at the terminal C atom.Soft inorganic nucleophiles -, SCN-> are added to form the zwitterionic complexes FeCo2(CO)9(μ3-C-CH2-Nu) (4,7,8) as proved by the structure determination of FeCo2(CO)9(μ3-C-CH2-PMe3) (4a).The products are of low thermal stability.Upon heating, the PR3 derivatives rearrange to the CO substitution products FeCo2(CO)8(PR3)(μ3-C=CH2) (5,6).C-C coupling is achieved by addition of malonic ester anion derivatives - (X = MeO2C, CN, Br).The anionic addition product for X = MeO2C (10a) can be protonated to form HFeCo2(CO)93C-CH2-CH(COOMe)2> (11) which liberates H2 upon warming resulting in FeCo2(CO)93-C=CH-CH(COOMe)2> (12).Thus, a substitution of a vinylidene H atom has been performed by an HX addition/H2 elimination sequence.Phosphorus ylides R3P=CHX are also added with C-C coupling to yield the complexes FeCO2(CO)9(μ3-C-CH2-CHX-PR3) (15, 16).The structure determination of the compounds with X = EtO2C and R = Ph (16 c) proves that these complexes differ from the complexes 4 just by insertion of one methylene unit.
