
Journal of the Chemical Society, Dalton Transactions p. 1323 - 1332 (1996)
Update date:2022-09-26
Topics:
Begley, Michael J.
Mountford, Philip
Stewart, Philip J.
Swallow, Daniel
Wan, Susan
Reaction of Li[C5H4Fe(C5H5)] with 2,3,4,5-tetramethylcyclopent-2-enone followed by acid work-up afforded the ferrocenyl-substituted cyclopentadiene [Fe(C5H5)(C5H4C5Me 4H)] 1. Lithiation of 1 with LiBun in hexane gave Li[C5Me4C5H4Fe(C5H 5)]. Reactions of this salt or the previously described lithium 3,4-dimethylcyclppentadienide or indenide homologues, Li[C5H2Me2C5H4Fe(C 5H5)] or Li[C9H6C5H4Fe(C5H 5)], with the allyl complexes [MoBr(MeCN)2(CO)2(η-C3H5)] or [WCl(MeCN)2(CO)2-(η-C3H5)] led to the corresponding fulvalene (and related)-bridged, Fe-Mo or Fe-W heterobimetallic derivatives [(C5H5)Fe(C5H4C5Me 4)Mo(CO)2(η-C3H5)] 2, [(C5H5)Fe(C5H4C5H 2Me2)M(CO)2(η-C3H5)] (M = Mo 3 or W 4) and [(C5H5)Fe(C5H4C9H 6)M(CO)2(η-C3H5)] (M = Mo 5 or W 6). The crystal structure of 5 has been determined. Reaction of the cinnamyl complex [MoBr(MeCN)2(CO)2(η-C3H4Ph)] with Li[C5H2Me2-C5H4Fe(C 5H5)] or Li[C9H6C5H4Fe(C5H 5)] yielded [(C5H5)Fe(C5H4C5H 2Me2)Mo(CO)2(H-C3H4Ph)] 7 or [(C5H5)Fe(C5H4C9H 6)Mo(CO)2(η-C3H4Ph)] 8 respectively, both of which exist as a mixture of isomers. Treatment of 7 with [Cr(CO)6] in Bun2O-tetrahydrofuran gave the Fe-Mo-Cr heterotrimetallic complex [(C5H5)Fe(CH4C5H2Me 2)(OC)2Mo(μ-η3:η6-C 3H4Ph)Cr(CO)3] 9. The new monometallic analogue [Mo(CO)2-(η-C3H5)(η-CMe5)] 10 has also been prepared. Cyclic voltammetric studies of some of the new heterobimetallic complexes and of 10, [Mo(CO)2(η-C3H5)(η -C5H5)] and [Mo(CO)2(η-C3H5)(η-C9H 7)] are described.
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