Catalytic macrocyclization of 3-methylthietane by Re{sub 2}(CO){sub 9} (SCH{sub 2}CHMeCH{sub 2}) and W(CO){sub 5}(SCH{sub 2}CHMeCH{sub 2})
- Univ. of South Carolina, Columbia, SC (United States)
The new compounds Re{sub 2}(CO){sub 9}SCH{sub 2}CHMeCH{sub 2}) (2) and W(CO){sub 5}(SCH{sub 2}CHMeCH{sub 2}), 8, have been prepared by the reactions of Re{sub 2}(CO){sub 9}(NCMe) (1) and W(CO){sub 5}(NCMe) (7) with 3-methylthietane, (SCH{sub 2}CHMeCH{sub 2}, 3-MT). Compounds 1, 2, 7, and 8 have been found to react with SCH{sub 2}CHMeCH{sub 2} at reflux to yield substantial amounts of the polythioether macrocycle 3,7,11-trimethyl-1,5,9-trithiacyclododecane (Me{sub 3}12S3) by a macrocyclization process consisting of a metal-induced ring-opening cyclooligomerization of three molecules of 3-MT. Me{sub 3}12S3 is formed as two isomers, cis,trans,trans-3,7,11-trimethyl-1,5, 9-trithiacyclododecane (c,t,t-Me{sub 3}12S3, 3) and cis,cis,cis-3,7, 11-trimethyl-1,5,9-triacyclododecane (c,c,c-Me{sub 3}12S3, 4), due to different orientations of the methyl substituents in the ring. A comparison of the two catalysts shows that the rhenium catalyst exhibits a higher activity and higher selectivity for the formation of Me{sub 3}12S3 than the tungsten complex. The reactions of 1 with 3 and 4 have yielded the new compounds Re{sub 2}(CO){sub 9}(c,t,t-SCH{sub 2}CHMe(CH{sub 2}SCH{sub 2}CHMe){sub 2}CH{sub 2}) (5) and Re{sub 2}(CO){sub 9}(c,c,c-SCH{sub 2}CHMe(CH{sub 2}SCH{sub 2}CHMe){sub 2}CH{sub 2}) (6), respectively. The molecular structures (of the free molecule 3 and the complexes 5 and 6 were established by single-crystal X-ray diffraction analyses. 14 refs., 4 figs.
- OSTI ID:
- 249564
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 10 Vol. 15; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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