109151-75-9Relevant academic research and scientific papers
Ligand rearrangements in dinuclear iron carbonyl complexes. A novel delocalized bridging vinylcarbene complex
Hoke, Jeffrey B.,Dewan, John C.,Seyferth, Dietmar
, p. 1816 - 1819 (1987)
Reaction of [Li] [(μ-CO)(μ-RS)Fe2(CO)6] salts with ethoxyacetylene followed by reaction of the anionic intermediate with an electrophile yields bridging vinylcarbene or bridging α,β-unsaturated acyl products resulting from unusual intramolecular rearrangement chemistry involving vinyl and carbonyl ligands.
Novel products from reactions of Li[(μ-CO)(μ-RS)Fe2(CO)6] salts with ethoxyacetylene
Seyferth, Dietmar,Hoke, Jeffrey B.,Dewan, John C.,Hofmann, Peter,Schnellbach, Michael
, p. 3452 - 3464 (2008/10/08)
Reactions of Li[(μ-CO)(μ-RS)Fe2(CO)6] salts with ethoxyacetylene followed by reaction of the anionic intermediate thus generated with acetyl or benzoyl chloride gave an Fe2(CO)6 complex that contained the thiolate ligand as well as a novel resonance-stabilized bridging vinylcarbene ligand which incorporated the acetylene and an original CO ligand that may be written as -C(OEt)=CHC(O2CR1)= ? =C(OEt)CH=C(O2CR1)-. The structure of the complex in which R = t-Bu and R1 = CH3 was determined by X-ray diffraction. Extended Hu?ckel MO calculations for a model system, Fe2(CO)6(μ-SH)(μ-C3H3), led to its description in terms of an ideally delocalized C3 bridge coupled to the iron atoms of the (μ-HS)Fe2(CO)6 unit by two strong σ-bonds and by moderate π-back-bonding. Protonation of the anionic intermediate with trifluoroacetic acid gave the α,β-unsaturated bridging acyl complexes (μ-EtOC(=CH2)C=O)(μ-RS)Fe2(CO)6 (R = t-Bu, Et). The X-ray crystal structure of the complex in which R = t-Bu was determined. These complexes lost CO in THF solution at room temperature, giving (μ-EtOC=CH2)(μ-RS)Fe2(CO)6.
