950860-92-1Relevant academic research and scientific papers
Snapshot of a chelation-assisted C-H/alkyne coupling: A ruthenium complex caught in the act of C-C bond formation
Benhamou, Laure,Cesar, Vincent,Lugan, Noel,Lavigne, Guy
, p. 4673 - 4676 (2007)
The complex Ru(CO)2(PPh3 )2 (1) reacts with o-(diphenylphosphanyl)benzaldehyde within 2 min at 20 °C to give the hydrido acyl complex Ru(H){P(C6H5 )2 (C 2 H4 )C(O))(CO)2 (PPh2 ) (2) via selective activation of the C-H bond of the aldehyde function. Further addition of diphenylacetylene (110 °C, 3 h) affords the novel complex Ru{P(C 6 H5 )2 (C6 H4 )C(O)(C6 H5 )C==CH(C6H5 )}(CO){P(C6 H5 )3 } (3), incorporating the newly assembled o-(diphenylphosphanyl)phenyl (E)-stilbenyl ketone ligand. The α,β-unsaturated ketone moiety of the latter is bound to the metal in an η4 coordination mode involving both a side-on coordination of the carbonyl group and a more classical η2 linkage of the olefinic bond. Both complexes were fully characterized by spectroscopic methods and by X-ray diffraction. The whole reaction sequence provides a valuable experimental model for the chelation-assisted hydroacylation of an alkyne with a tethered aldehyde.
