Facile alkyne coupling reactions in dirhenium carbonyl complexes
- Univ. of South Carolina, Columbia (United States)
The complex (OC)[sub 4]Re[trans-[mu]-HC=C(CO[sub 2]Me)]Re(CO)[sub 5] (1) was converted to the reactive acetonitrile complex (OC)[sub 4]Re[trans-[mu]-HC=C(CO[sub 2]Me)]Re(CO)[sub 4](NCMe) (2) by reaction with Me[sub 3]NO in acetonitrile. Under an atmosphere of CO, complex 2 reacts with HC[triple bond]CO[sub 2]Me in refluxing CH[sub 2]Cl[sub 2] to yield the new complexes (OC)[sub 4]Re[[mu]-C(H)=C(CO[sub 2]Me)C(H)=C(CO[sub 2]Me)]-Re(CO)[sub 5] (3; 11%) and (OC)[sub 4]Re[C(H)=C(CO[sub 2]Me)C(H)=C(CO[sub 2]Me)C(H)= C(CO[sub 2]Me)]Re(CO)[sub 4] (4a,b; 49%, existing in solution as a mixture of isomers) by the head-to-tail coupling of two and three HC[equivalent to]CCO[sub 2]Me molecules, respectively. In the absence of CO only compound 4 and a small amount of the new compound [ovr Re(CO)[sub 4][C[sup 6]H[sub 2](CO][sub 2]Me)(CO[sub 2]Me)[sub 2]] (5;6%) were obtained. Complex 3 was converted into 4 by reaction with additional HC[equivalent to]CCO[sub 2]Me in the presence of Me[sub 3]NO. When heated to 98[degrees]C, 4 was transformed into 5 in 22% yield. Three of the products, 3, 4a, and 5 were characterized crystallographically. In complex 3 the two linked HC[equivalent to]CCO[sub 2]Me groups form a four-carbon chain between the metal-containing groups. One of the carboxylate substituents is also coordinated to form a five-membered metallacyclic ring. In complex 4a the metal-containing groups are joined by a six-carbon chain formed from the three alkynes, and two of the carboxylate groups are coordinated to form five- and six-membered metallacyclic rings. The six-carbon chain in 4 was transformed into a 2,4,6-tris(methoxycarbonyl)phenyl group that is [sigma]-coordinated to the metal atom and also has one of its carboxylate groups coordinated. 10 refs., 3 figs., 6 tabs.
- OSTI ID:
- 5989623
- Journal Information:
- Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 12:5; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
360601 -- Other Materials-- Preparation & Manufacture
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
CRYSTALLOGRAPHY
DATA
EXPERIMENTAL DATA
INFORMATION
MOLECULAR STRUCTURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES