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 )
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), Vol. 111:9; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
CRYSTAL STRUCTURE
PHOTOLYSIS
PROPYLENE
RHENIUM COMPLEXES
CHEMICAL BONDS
EXPERIMENTAL DATA
ISOMERS
PHOTOCHEMISTRY
X-RAY DIFFRACTION
ALKENES
CHEMICAL REACTIONS
CHEMISTRY
COHERENT SCATTERING
COMPLEXES
DATA
DECOMPOSITION
DIFFRACTION
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
SCATTERING
TRANSITION ELEMENT COMPLEXES
400500* - Photochemistry