Cyclobutyne ligands. 3. Synthesis and characterization of a disubstituted cyclobutyne ligand in the triosmium complex Os[sub 3](CO)[sub 9][([mu][sub 3]-[eta][sup 2]-C[sub 2]CH[sub 2]C(Me)[sup t]Bu)]([mu][sub 3]-S)

Journal Article · Fri Oct 01 04:00:00 EDT 1993 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00034a054· OSTI ID:5526110

Adams, R D; Qu, X; Wu, W ^[1]

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1. Univ. of South Carolina, Columbia, SC (United States)

The reaction of 4-tert-butyl-4-methyl-1-(phenylthio)cyclobutene with Os[sub 3](CO)[sub 10]/(NCMe)[sub 2] at 25[degrees]C yielded the new complex Os[sub 3](CO)[sub 10]/[[mu]-PhSC[sub 2]CH[sub 2]C(Me)[sup t]Bu]([mu]-H), 3 (54% yield), by displacement of the MeCN ligands and the addition of the 4-tert-butyl-4-methyl-1-(phenylthio)-cyclobutene and the activation of the alkenyl CH bond. Compound 3 was decarbonylated by refluxing in heptane solvent (97[degrees]C) to yield the new compound Os[sub 3](CO)[sub 9][[mu][sub 3]-SPhC[sub 2]CH[sub 2]C(Me)[sup t]Bu]([mu]-H), 4 (93%), in which the alkenyl double bond of the metalated cyclobutenyl ligand has become coordinated to the cluster. When heated to 125[degrees]C, compound 4 was transformed to the new complex Os[sub 3](CO)[sub 9]([mu][sub 3]-[eta][sup 2]-C[sub 2]CH[sub 2]C(Me)[sup t]B u)([mu][sub 3]-S), 5 (60% yield based on 4 consumed). Compound 5 contains a triply bridging 3-methyl-3tert-butylcyclobutyne ligand formed from the metalated cyclobutenyl ligand by cleavage from the sulfur atom in 4. The phenyl group was also cleaved from the sulfur atom, resulting in the formation of a triply bridging sulfido ligand. The phenyl group and hydride ligand were eliminated, presumably as benzene. 18 refs., 3 figs., 10 tabs.

• OSTI ID: 5526110
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 12:10; 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
ALKYNES
CARBONYLS
CHEMICAL REACTIONS
COMPLEXES
COUPLING
CRYSTAL STRUCTURE
CYCLOALKYNES
HYDROCARBONS
LIGANDS
MOLECULAR STRUCTURE
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OSMIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES