η-1,2,4,6-Tetramethylcycloheptatrienyl molybdenum chemistry
- 1 January 1993
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 1,p. 17-21
- https://doi.org/10.1039/dt9930000017
Abstract
Treatment of [Mo(CO)6] with 1,3,5,7-tetramethylcycloheptatriene in octane gives a mixture of [Mo(η6-C7H4Me4-1,3,5,7)(CO)3]1, [Mo(η6-C7H4Me4-1,2,4,6)(CO)3]2 and [Mo(η6-C7H4Me4-1,3,4,6)(CO)3]3. The compounds 2 and 3 arise as a result of sequential 1,5-shifts of the 7-endo-hydrogen atom of the initially formed 1. Hydride abstraction from compounds 1–3 by [CPh3][BF4] gives [Mo(η7-C7H3Me4-1,2,4,6)(CO)3][BF4]4. Compound 4 reacts with LiCl to yield [Mo(η7-C7H3Me4-1,2,4,6)(CO)2Cl]5 which reacts with 1 equivalent of Me2PCH2CH2PMe2(dmpe) to give [Mo(η3-C7H3Me4-1,2,4,6)(dmpe)(CO)2Cl]7. This is fluxional due to trigonal twist rearrangement and 1,2-shift of metal around the C7 ring. Photolysis of 7 in toluene produces [Mo(η7-C7H3Me4-1,2,4,6)(dmpe)Cl]9. Treatment of 4 with toluene affords the mixed-sandwich compound [Mo(η6-C6H5Me)(η7-C7H3Me4-1,2,4,6)][BF4]10 which yields [Mo(η7-C7H3Me4-1,2,4,6)(CH3COCHCOCH3)(PPh3)]11 upon treatment with sodium pentane-2,4-dionate and triphenylphosphine.Keywords
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