Reactions of Mn{sub 2}(CO){sub 9}(NCMe) with alkynes containing electron-donating substituents
- Univ. of South Carolina, Columbia, SC (United States)
The addition of the electron-rich alkynes, MeC{triple_bond}CX, X = NMe{sub 2} or OEt, to the dimanganese complex Mn{sub 2}(CO){sub 9}(NCMe), 1, has yielded the vinylidene complexes Mn{sub 2}(CO){sub 8}[{mu}-{eta}{sup 2}-C=C-(Me)C=O(X)], 2a, X = NMe{sub 2}, and 2b, X = OEt, respectively, by an addition and a rearrangement of the alkyne that included a CO insertion step. Both products will also add 1 equiv of MeCP{triple_bond}CNMe{sub 2} to form the complexes Mn{sub 2}(CO){sub 7}[{mu}-{eta}{sup 2}-CC(Me)C(NMe{sub 2})C(Me)C=O(X)], 3a, X = NMe{sub 2}, and 3b, X = OEt, which contain a four-membered carbocyclic ring formed by the addition of the C-C triple bond across the C-C double bond of the vinylidene ligand. The carbocyclic ring in complex 3a was opened thermally at 80 {degrees}C to yield the complex Mn{sub 2}(CO){sub 6-} [{mu}-{eta}{sup 5}-(Me{sub 2}N) CC(Me)CC(Me)C=O (NMe{sub 2})], 4, that contains a carbene center. It was also opened by treatment with acetic acid to yield the mononuclear metal complex Mn(CO){sub 3}({eta}{sup 2}-O{sub 2}CMe), 7. Compounds 2a, b, 3a, 4, and 5 were characterized by single-crystal X-ray diffraction analyses.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 433551
- Journal Information:
- Organometallics, Vol. 12, Issue 7; Other Information: PBD: Jul 1993
- Country of Publication:
- United States
- Language:
- English
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