Coordination of polythiaether macrocycles to metal cluster complexes. 3. Synthesis, structure, and dynamical activity of the cluster complexes Ru{sub 3}(Co){sub 7}({mu}-CO){sub 2} (1,1,1-{eta}{sup 3}-12S3) and Ru{sub 3}(CO){sub 7}({mu}-CO){sub 2} (1,1,1-{eta}{sup 3}-9S3)
- Univ. of South Carolina, Columbia, SC (United States)
The compounds Ru{sub 3}(CO){sub 7}({mu}-CO){sub 2} (1,1,1-{eta}{sup 3}-12S3), 1 (12S3 = 1,5,9-trithiacyclododecane), and Ru{sub 3}(CO){sub 7}({mu}-CO){sub 2} (1,1,1-{eta}{sup 3}-9S3), 2 (9S3 = 1,4,7-trithiacyclononane), were obtained in 83% yields from the reactions of Ru{sub 3}(CO){sub 12} with 12S3 and 9S3, respectively. Both compounds were characterized crystallographically and were shown to possess Fe{sub 3}(CO){sub 12}-like structure having two bridging CO ligands across one of the RU-Ru bonds and tridentate 12S3 and 9S3 ligands, respectively. Both compounds exhibit dynamical ligand activity on the NMR time scale at 25{degree}C. The dynamical activity of the CO ligands in 1 was characterized in detail by {sup 13}C NMR spectroscopy through a combination of variable temperature and eXSY magnetization transfer measurements. There is evidence for at least two mechanisms. The lowest temperature process can be explained by a series of bridge-terminal exchange processes involving the CO ligands. Compound 2 was transformed into the new compound Ru{sub 2}(CO){sub 6}({mu}-{eta}{sup 2}-SCH{sub 2}CH{sub 2}S), 3 (16%), and the known compound Ru{sub 3}(CO){sub 9} ({mu}-{eta}{sup 3}-SCH{sub 2}CH{sub 2}SCH{sub 2}-CH{sub 2}S), 4 (32%), by degradation of the 9S3 ligand when solutions in THF solvent were heated to reflux. Crystal data for 1 and 2 are provided. 17 refs., 4 figs., 7 tabs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 102879
- Journal Information:
- Organometallics, Vol. 14, Issue 8; Other Information: PBD: Aug 1995
- Country of Publication:
- United States
- Language:
- English
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Coordination of polythiaether macrocycles to metal cluster complexes. 2. Coordination of polythiaether macrocycles to hexaruthenium carbido carbonyl clusters
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