Dimetalated olefins formed by the insertion of an alkyne into an Re-Re bond. The reaction of EtO[sub 2]CC[triple bond]CCO[sub 2]Et with Re[sub 2](CO)[sub 9](NCMe)
- Univ. of South Carolina, Columbia, SC (United States)
The complex Re(CO)[sub 4][[mu]-(Z)-(EtO[sub 2]C)C=C(CO[sub 2]Et)]Re(CO)[sub 5], 2, obtained from the reaction of Re[sub 2](CO)[sub 9](NCMe), 1, with EtO[sub 2]CC[triple bond]CCO[sub 2]Et was analyzed by single crystal X-ray diffraction analysis and was found to be a Z-dimetalated olefin complex formed by the insertion of the alkyne into the rhenium--rhenium bond. One of the carboxylate groups is coordinated to one of the rhenium atoms through the ketonic oxygen atom to form a four membered metallacyclic ring. The absence of crossover in a reaction of a mixture of fully [sup 13]CO labeled 1 and unlabeled 1 indicates that the insertion of the alkyne into the metal-metal bond occurs by an intramolecular mechanism. When irradiated (UV-vis), compound 2 was isomerized to the complex Re(CO)[sub 4][[mu]-(E)-(EtO[sub 2]C)C=C(CO[sub 2]Et)]Re(CO)[sub 5 ],3, and the ketonic oxygen atom of the carboxylate group became coordinated to the other rhenium atom to form a five membered metallacyclic ring. Decarbonylation of 3 by irradiation yielded the new complex Re(CO)[sub 4][[mu]-(E)-(EtO[sub 2]C)C=C(CO[sub 2]Et)]Re(CO )[sub 4], 4, by coordination of the oxygen atom of the second carboxylate group. 8 refs., 5 figs., 6 tabs.
- OSTI ID:
- 7019613
- Journal Information:
- Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 13:4; ISSN 0276-7333; ISSN ORGND7
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
ALKENES
ALKYNES
CARBONYLS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPILED DATA
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
ELECTROMAGNETIC RADIATION
HYDROCARBONS
INFORMATION
ISOMERIZATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RADIATION EFFECTS
RADIATIONS
RHENIUM COMPLEXES
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET RADIATION
VISIBLE RADIATION
X-RAY DIFFRACTION