Reactions of the iridathiabenzene complex Cp{sup *}Ir(2,5-dimethylthiophene) with Co{sub 2}(CO){sub 8}, Co{sub 4}(CO){sub 12}, and ({eta}{sup 6}-C{sub 6}H{sub 3}Me{sub 3})Co{sub 4}(CO){sub 9}
- Iowa State Univ., Ames, IA (United States)
With the goal of preparing an {eta}{sup 6}-iridathiabenzene complex of Co{sub 4}(CO){sub 12}, the ring-opened iridathiabenzene complex Cp{sup *}Ir(C,S-2,5-Me{sub 2}T) (1), where 2,5-Me{sub 2}T is 2,5-dimethylthiophene, was reacted with Co{sub 4}(CO){sub 12}, Co{sub 2}(CO){sub 8}, and ({eta}{sup 6}-C{sub 6}H{sub 3}Me{sub 3})Co{sub 4}(CO){sub 9}. Only in the reaction of ({eta}{sup 6}-C{sub 6}H{sub 3}Me{sub 3})Co{sub 4}(CO){sub 9} under mild conditions (35-40{degree}C) was the {eta}{sup 6}-iridathiabenzene cluster [{eta}{sup 6}-Cp{sup *}Ir(C,S-2,5-Me{sub 2}T)]Co{sub 4}(CO){sub 9} (7) obtained. At higher temperatures, the reaction yielded Cp{sup *}Ir({eta}{sup 4}-2,5-Me{sub 2}T.Co{sub 4}(CO){sub 11}) (6), in which the 2,5-Me{sub 2}T ligand is coordinated through its diene to the Ir and through its sulfur to a Co of the cluster. Reactions of Co{sub 4}(CO){sub 12} and Co{sub 2}(CO){sub 8} with 1 yielded Cp{sup *}Ir({eta}{sup 4}-2,5-Me{sub 2}T.Co{sub 4})(CO){sub 11} (2), an isomer of 6, which converts to the desulfurized linear tetranuclear cluster [Cp{sup *}Ir(C(Me)=CHCH=C(Me))({mu}-CO){sub 2}Co]{sub 2} (3); this species contains bridging iridacyclopentadiene units. Cluster 3 has a structure with a Co{sub 2}({mu}-Co){sub 2} core and Cp{sup *}Ir(C(Me)=CHCH=C(Me))(CO) (4) end groups. In fact, 3 can be prepared form Co{sub 2}(CO){sub 8} and 4. Molecular structures of 2-4 are reported, together with a discussion of pathways that lead to their formation. 30 refs., 3 figs., 7 tabs.
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 226765
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 5 Vol. 15; ISSN 0276-7333; ISSN ORGND7
- Country of Publication:
- United States
- Language:
- English
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