University of Illinois Urbana-Champaign

Alkylidene Dirhodium Chemistry

Dimas, Peter Allan

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Description

Title
Alkylidene Dirhodium Chemistry
Author(s)
Dimas, Peter Allan
Issue Date
1983
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Inorganic
Abstract
  • Alkylidene-bridged complexes have been prepared from unsaturated dirhodium complexes and diazo compounds. Several aspects of the reactivity of the alkylidene group in these and related complexes have been examined.
  • The unsaturated complex {((eta)('5)-C(,5)Me(,5))(,2)Rh(,2)((mu)-CO)}(,2) reacts with diazo compounds to form the (mu)-alkylidene complexes {((eta)('5)-C(,5)Me(,5))(,2)Rh(,2)(CO)(,2)((mu)-CRR')}. Thermolysis of {((eta)('5)-C(,5)Me(,5))(,2)Rh(,2)(CO)(,2)((mu)-CPh(,2))} results in decarbonylation to give {((eta)('5)-C(,5)Me(,5))(,2)Rh(,2)((mu)-CO)((mu)-CPh(,2))}. The unsaturated complex {((eta)('5)-C(,5)Me(,5))(,2)Rh(,2)((mu)-NO)((mu)-CO)}BF(,4) has been prepared from {((eta)('5)-C(,5)Me(,5))Rh(CO)(,2)} and NOBF(,4). It also reacts with diazo compounds (-78(DEGREES)C) to form (mu)-alkylidene complexes which decarbonylate upon warming to room temperature resulting in the novel series of unsaturated complexes {((eta)('5)-C(,5)Me(,5))(,2)Rh(,2)((mu)-NO)((mu)-CRR')}BF(,4). Acetylene inserts into the metal-alkylidene bonds of {((eta)('5)-C(,5)Me(,5))(,2)Rh(,2)((mu)-NO)((mu)-CHPh)}BF(,4) to form the stable vinylmethylidene compound {((eta)('5)-C(,5)Me(,5))(,2)Rh(,2)((mu)-NO)((mu)-(eta)('1),(eta)('3)-CHCHCHPh)}BF(,4).
  • The bis-alkylidene complex(' ){((eta)('5)-C(,5)Me(,5))(,2)Rh(,2)((mu)-C(H)C(OEt)OC-(H)CO(,2)Et)((mu)-NO)}BF(,4) has been prepared from {((eta)('5)-C(,5)Me(,5))(,2)Rh(,2)((mu)-NO)((mu)-CO)}BF(,4) and ethyl diazoacetate. The terminal and bridging alkylidene moieties in this complex are condensed into a unique metallocyclic ligand. Heating a solution of this complex under a carbon monoxide atmosphere induces coupling of the alkylidene moieties to form an alkene. Crossover experiments have provided evidence for an intramolecular coupling mechanism.
  • Treatment of {((eta)('5)-C(,5)H(,5))(,2)Rh(,2)(CO)(,2)((mu)-CHR)} (R = H, Me) with trifluoroacetic acid causes disproportionation to give CH(,3)R, {((eta)('5)-C(,5)H(,5))Rh(CO)(,2)} and the novel cationic alkylidyne clusters {((eta)('5)C(,5)H(,5))(,3)Rh(,3)((mu)-CO)(,2)((mu)(,3)-CR)}('+).
Graduation Semester
1983
Type of Resource
text
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http://hdl.handle.net/2142/72264

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