Cyclobutyne ligands. 5. C-H bond cleavage versus ring opening of [sigma],[pi]-coordinated cyclobutenyl ligands
- Univ. of South Carolina, Columbia, SC (United States)
The reaction of 1-bromocyclobutene with Os[sub 3](CO)[sub 10](NCMe)[sub 2] at 25 [degree]C yielded two new complexes: Os[sub 3](CO)[sub 10]([mu]-Br)([mu]-[ovr CCHCH[sub 2]C]H[sub 2]) (1; 44%) and Os[sub 3](CO)[sub 9]([mu]-Br)([mu][sub 3]-CCHCH[sub 2]CH[sub 2]) (2; 16%). Compound 1 contains a bridging [sigma], [pi]-coordinated cyclobutenyl and a bridging bromo ligand across the open edge of a triosmium cluster. Compound 2 contains a metalated [sigma], [pi]-coordinated bridging alkenyl ligand. Compound 2 was obtained from 1 in good yield both by thermal- and irradiation-induced ring-opening cleavage of a carbon-carbon bond of the cyclobutenyl ligand. Compound 1 was decarbonylated by treatment with Me[sub 3]NO at 0 [degree]C and was converted into a mixture of 2 (37 %) and the new compound Os[sub 3](CO)[sub 9]([mu]-Br)([mu][sub 3]-[eta][sup 2]-[ovr C[sub 2]CH[sub 2]C]H [sub 2])-([mu]-H) (3; 8%). Compound 3 contains a new example of a triply bridging cyclobutyne ligand formed by the transfer of the alkenyl hydrogen atom of the cyclobutenyl ligand to the metal atoms. Interestingly, compound 3 could not be transformed to 2 by either thermal or photochemical methods. Crystal data for 1 are supplied. 14 refs., 3 figs., 10 tabs.
- OSTI ID:
- 7019575
- Journal Information:
- Organometallics; (United States), Vol. 13:5; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ORGANIC BROMINE COMPOUNDS
CHEMICAL REACTIONS
ORGANOMETALLIC COMPOUNDS
OSMIUM COMPLEXES
CHEMICAL BONDS
COMPILED DATA
CYCLOALKYNES
DECARBOXYLATION
INFRARED SPECTRA
LIGANDS
NUCLEAR MAGNETIC RESONANCE
PHOTOLYSIS
PYROLYSIS
THIN-LAYER CHROMATOGRAPHY
ULTRAVIOLET RADIATION
X-RAY DIFFRACTION
ALKYNES
CHROMATOGRAPHY
COHERENT SCATTERING
COMPLEXES
DATA
DECOMPOSITION
DIFFRACTION
ELECTROMAGNETIC RADIATION
HYDROCARBONS
INFORMATION
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
RADIATIONS
RESONANCE
SCATTERING
SEPARATION PROCESSES
SPECTRA
THERMOCHEMICAL PROCESSES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures
400500 - Photochemistry