Cyclobutyne ligands. 5. C-H bond cleavage versus ring opening of [sigma],[pi]-coordinated cyclobutenyl ligands

Journal Article · Sun May 01 00:00:00 EDT 1994 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00017a065· OSTI ID:7019575

Adams, R D; Chen, L; Qu, X ^[1]

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1. 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), Journal Name: Organometallics; (United States) Vol. 13:5; ISSN 0276-7333; ISSN ORGND7
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
ALKYNES
CHEMICAL BONDS
CHEMICAL REACTIONS
CHROMATOGRAPHY
COHERENT SCATTERING
COMPILED DATA
COMPLEXES
CYCLOALKYNES
DATA
DECARBOXYLATION
DECOMPOSITION
DIFFRACTION
ELECTROMAGNETIC RADIATION
HYDROCARBONS
INFORMATION
INFRARED SPECTRA
LIGANDS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OSMIUM COMPLEXES
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PYROLYSIS
RADIATIONS
RESONANCE
SCATTERING
SEPARATION PROCESSES
SPECTRA
THERMOCHEMICAL PROCESSES
THIN-LAYER CHROMATOGRAPHY
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET RADIATION
X-RAY DIFFRACTION