Photochemical carbonylation of benzene by iridium(I) and rhodium(I) square-planar complexes
The photochemical carbonylation of unfunctionalized arene C-H bonds is catalyzed by various d/sup 8/ complexes under low CO pressure at ambient temperature. The carbonylation of benzene to benzaldehyde is achieved by using IrH(CO)/sub 2/(dppe), IrH/sub 3/(CO)(dppe), or IrBr(CO)(dppe) as the catalyst, and the photoactive species in each case appears to be IrX(CO)(dppe) (X = H or Br). The monodentate phosphine complexes MCl(CO)(PPh/sub 3/)/sub 2/ (M = Rh, Ir) exhibit similar photochemical activity leading to benzene carbonylation. In all cases the amount of benzaldehyde formed is limited by thermodynamics with /Delta/G/sub 298//degree/ = +1.7 kcal. When RhCl(CO)(PPh/sub 3/)/sub 2/ is placed under /sup 13/CO with PhCHO, photochemical decarbonylation is achieved along with significant /sup 13/CO incorporation into the aldehyde, confirming the occurrence of both carbonylation and decarbonylation. Both processes are thought to involve the same initial photochemical step of ligand dissociation to generate a 14e intermediate.
- Research Organization:
- Univ. of Rochester, NY (USA)
- OSTI ID:
- 5913280
- Journal Information:
- Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 7:10; ISSN ORGND
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400500* -- Photochemistry
ALDEHYDES
AROMATICS
BENZALDEHYDE
BENZENE
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLATION
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
IRIDIUM COMPLEXES
LOW PRESSURE
MEDIUM TEMPERATURE
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
RHODIUM COMPLEXES
SYNTHESIS
THERMODYNAMICS
TRANSITION ELEMENT COMPLEXES
YIELDS