Coupling of alkynes to carbon monoxide at a diamanganese center. A new route to carboxylate-functionalized pyrans

Journal Article · Wed May 18 04:00:00 EDT 1994 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00089a042· OSTI ID:7267414

Adams, R D; Chen, L ^[1]

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

Metal-mediated coupling reactions between alkynes and CO have led to a wide variety of new organic ligands and new organic molecules. Recent studies of the reactions of alkynes with dinuclear manganese carbonyl complexes have revealed a tendency for coupling of the alkynes to one or more of the CO ligands. A special feature of these reactions is the coordination of the oxygen atom of the CO group of the metal atoms. We have now found that the reaction of EtO[sub 2]CC[triple bond]CCO[sub 2]Et with Mn[sub 2](CO)[sub 9](NCMe) at 25[degree]C for 20 h produces the new compound Mn[sub 2](CO)[sub 8][EtO[sub 2]CC=C(CO[sub 2]Et)C=O], 1, in a 22% diffraction analysis, and an ORTEP diagram of its molecular structure is shown. The molecule contains a EtO[sub 2]CC=C(CO[sub 2]Et)C=O ligand formed by the coupling of the alkyne to the carbon atom of a CO ligand. Most importantly, the EtO[sub 2]CC=C(CO[sub 2]Et)C=O ligand has been inserted into the manganese-manganese bond. The oxygen atom of the CO group and one carbon atom of the EtO[sub 2]CC=CCO[sub 2]Et grouping are coordinated to the metal atom Mn(1), resulting in the formation of a five-membered metallacyclic ring. The carbon atom of the CO group and the carbonyl oxygen O(4) of one of the carboxylate groups are coordinated to Mn(2) to form a second five-membered metallacyclic ring. 15 refs., 2 figs.

• OSTI ID: 7267414
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 116:10; ISSN JACSAT; ISSN 0002-7863
• 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 REACTIONS
COHERENT SCATTERING
DIFFRACTION
ELECTROMAGNETIC RADIATION
ESTERS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
LIGANDS
MAGNETIC RESONANCE
MANGANESE COMPOUNDS
MOLECULAR STRUCTURE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PYRANS
RADIATIONS
RESONANCE
SCATTERING
TRANSITION ELEMENT COMPOUNDS
ULTRAVIOLET RADIATION
X-RAY DIFFRACTION