92940-69-7Relevant academic research and scientific papers
Decomposition Reactions of Cationic Ruthenium Formyl Complexes
Smith, Garry,Cole-Hamilton, David J.
, p. 1203 - 1208 (1984)
trans- (dppe=Ph2PCH2CH2PPh2) decomposes in CH2Cl2 with first-order kinetics (t1/2=9.25 min, k=11x10-4 s-1) to give cis- which subsequently isomerises to the trans isomer (t1/2 ca. 72 h).A deuterium isotope effect of 1.8 on the decomposition reaction is interpreted as being primary, the low value being attributable to a three-membered cyclic trasition state and a movement of the oxygen atom during the rate-determining step.A predissociation of a phosphorus atom of a dppe ligand is followed by rate-determining hydride migration for the decomposition, or fluxionality of the five-membered intermediate for the isomerisation.If the isomerisation of cis- is carried out at low temperature, significant H/D exchange of the deuteride and both phenyl and methylene hydrogen atoms of the dppe ligand is observed. cis- (dppm=Ph2PCH2PPh2) gives with a unidentate dppm ligand but chelation occurs on photolysis in CH2Cl2 to give trans- via trans-.
