Photochemical C-H bond activation of coordinated propene in (. eta. sup 5 -C sub 5 Me sub 5 )Re(CO) sub 2 (. eta. sup 2 -C sub 3 H sub 6 ). X-ray structure determination of exo and endo isomers of the resulting. eta. sup 3 -allyl(hydrido) complex (. eta. sup 5 -C sub 5 Me sub 5 )Re(H)(CO)(. eta. sup 3 -C sub 3 H sub 5 )
Journal Article
·
· Journal of the American Chemical Society; (USA)
One mechanism that has been implicated in the transition-metal-catalyzed isomerization of alkenes is the reversible formation of an {eta}{sup 3}-allyl (hydrido) intermediate (Scheme I) by oxidative addition of an allylic C-H bond to the metal. While a small number of well-characterized {eta}{sup 3}-allyl (hydrido) complexes have now been synthesized, in no case has the crucial step of allylic C-H activation been observed starting from the well-defined alkene complex. To their knowledge, only one previous study mentions the photochemical formation of an {eta}{sup 3}-allyl (hydrido) complex. Here they report that photolysis of the propene complex Cp*Re(CO){sub 2}(C{sub 3}H{sub 6}) (1) (Cp* = {eta}{sup 5}-C{sub 5}Me{sub 5}) results in the formation of the {eta}{sup 3}-allyl (hydrido) complex Cp*Re(CO)(H)({eta}{sup 3}-C{sub 3}H{sub 5}) (2). Furthermore, they have been successful in isolating the exo and endo isomers of 2, differing in the orientation of the {eta}{sup 3}-allyl group, and the structures of both have been determined by X-ray crystallography.
- OSTI ID:
- 5040967
- Journal Information:
- Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:9; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALKENES
CARBONYLS
CHEMICAL BONDS
CHEMICAL REACTIONS
CHEMISTRY
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DECOMPOSITION
DIFFRACTION
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
ISOMERS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
PROPYLENE
RHENIUM COMPLEXES
SCATTERING
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION
400500* -- Photochemistry
ALKENES
CARBONYLS
CHEMICAL BONDS
CHEMICAL REACTIONS
CHEMISTRY
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DECOMPOSITION
DIFFRACTION
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
ISOMERS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
PROPYLENE
RHENIUM COMPLEXES
SCATTERING
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION