Decomposition Reactions of Cationic Ruthenium Formyl Complexes

DOI: 10.1039/DT9840001203

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1203 - 1208 (1984)

Update date:2022-08-04

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Authors:

Smith, Garry

Cole-Hamilton, David J.

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Article abstract of DOI:10.1039/DT9840001203

trans- (dppe=Ph2PCH2CH2PPh2) decomposes in CH2Cl2 with first-order kinetics (t_1/2=9.25 min, k=11x10^-4 s^-1) to give cis- which subsequently isomerises to the trans isomer (t_1/2 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-.

Full text of DOI:10.1039/DT9840001203

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