Abstract
Mo2(η 3-μ 2-allyl)2(η 3-allyl)2, A, is an organometallic molybdenum dimer with a quadruple Mo-Mo bond. ButOH reacts with A to form propene concurrently with an NMR-detectable intermediate containing two types of t-butoxide ligands. At 0 °C, the intermediate is readily transformed into an isolable species, Mo4(η 3-μ 2-ally1)4(μ 2-OBut)4, with a proposed tetrametallacyclobutadiyne structure. The reaction of A with acetylacetone yields a pinkish product with concomitant evolution of propene having the structure, Mo(2 η 3 -μ 2-allyl)2(η 2 -acac)2. Acetylacetonates have replaced the terminal η 3 -allyls structurally in A leaving the Mo2(η 3 -μ 2-allyl)2 core intact. Carbon monoxide promotes the heretofore unobserved isomerization of green A to a violet isomer with configurational changes in the bonding of the bridging allyl ligands to the dimetal center. In addition carbon monoxide induces allyl dimerization upon reaction with A yielding η 4-1,5-hexadiene)Mo(CO)4 and eventually Mo(CO)6 and free 1,5-hexadiene as products.
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© 1990 Springer Science+Business Media New York
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Blau, R.J., Tsay, RJ., Ho, SI. (1990). Reactivity and Isomerization of Mo2(Allyl)4 . In: Fackler, J.P. (eds) Metal-Metal Bonds and Clusters in Chemistry and Catalysis. Industry-University Cooperative Chemistry Program Symposia. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-2492-6_25
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DOI: https://doi.org/10.1007/978-1-4899-2492-6_25
Publisher Name: Springer, Boston, MA
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