Reactions of [(CO){sub 3}Mn({eta}{sup 5}-Thi)]{sup +} (Thi = thiophene or 2,5-dimethylthiophene) with nucleophiles
- Iowa State Univ., Ames. IA (United States)
The {eta}{sup 5}-thiophene complexes, (CO){sub 3}Mn({eta}{sup 5}-T){sup +} (1) and [(CO){sub 3}Mn({eta}{sup 5}-2,5-Me{sub 2}T)]{sup +} (2), react with LiCuR{sub 2} (R = Me or Ph) by adding R{sup -} to the sulfur atom of the thiophene, which gives the {eta}{sup 4}-thiophene complexes, (CO){sub 3}Mn({eta}{sup 4}-T.R) and (CO){sub 3}Mn({eta}{sup 4}-2,5-Me{sub 2}T.R). An X-ray study of (CO){sub 3}Mn({eta}{sup 4}-T.C{sub 6}H{sub 5}) (6) shows the {eta}{sup 4}-T.C{sub 6}H{sub 5} ligand to be coordinated to the manganese through the four thiophene carbon atoms, while the sulfur bearing the phenyl group is bent away from the metal. The structure of 6 supports previous suggestions that the sulfur in {eta}{sup 5}-thiophene complexes is an electrophilic center. Reactions of 1 or 2 with RS{sup -}, CH{sub 3}O{sup -}, or {sup -}CH(CO{sub 2}CH{sub 3}){sub 2} nucleophiles result in the displacement of thiophene with the formation of [(CO){sub 4}Mn({mu}-SR)]{sub 2} or Mn{sub 2}(CO){sub 10}. The structure of [(CO){sub 4}Mn({mu}-SC{sub 6}H{sub 4}CH{sub 3}-p)]{sub 2}, established by X-ray studies, is also reported. 30 refs., 2 figs., 5 tabs.
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 196655
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 1 Vol. 15; ISSN 0276-7333; ISSN ORGND7
- Country of Publication:
- United States
- Language:
- English
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