Alkyne insertions into metal-metal bonds. Synthesis of heteronuclear dimetalated olefins by insertion of MeO{sub 2}CC=CCO{sub 2}Me into an Re-Fe single bond
- Univ. of South Carolina, Columbia, SC (United States)
Activation of the complex CpFe(CO){sub 2}Re(CO){sub 5}, 1, by Me{sub 3}NO followed by treatment with MeO{sub 2}CC=CCO{sub 2}Me yielded the Z-dimetalated olefin complex CpFe(CO){sub 2}[{mu}-(Z)-(MeO{sub 2}C)C=C(CO{sub 2}Me)]Re( CO){sub 4}, 2, in 78% yield. Compound 2 was isomerized to E-isomer CpFe(CO){sub 2}[{mu}-(E)-(MeO{sub 2}C)C-C(CO{sub 2}Me)]Re(CO) {sub 4}, 3, 18% yield, by heating solutions in heptane solvent to reflux for 70 min. When compound 2 was treated with MeO{sub 2}CC=CCO{sub 2}Me in heptane solvent at reflux, the metallacyclic complex CpFeRe(CO){sub 4}[{mu}-C(CO{sub 2}Me)C(CO{sub 2}Me)C(CO{sub 2}Me)C (CO{sub 2}Me)], 4, was formed in 59% yield. Compounds 2, 3, and 4 were characterized by single crystal x-ray diffraction analyses. Compound 2 is a Z-dimetalated olefin complex in which the carbonyl oxygen atom of one of the carboxylate groups is coordinated to the rhenium atom to form a four-membered ring. Compound 3 is an E-isomer of 2 in which the carbonyl oxygen atom of the other carboxylate group is coordinated to the rhenium atom to form a five-membered ring. In compound 4 the two alkynes are coupled to each other and to the rhenium atom to form a metallacycle that is {pi}-bonded to the iron atom. 13 refs., 3 figs., 4 tabs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 70372
- Journal Information:
- Organometallics, Vol. 14, Issue 6; Other Information: PBD: Jun 1995
- Country of Publication:
- United States
- Language:
- English
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