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- W2788536055 abstract "The reaction of a series of M·Zr heterobimetallic hydride complexes with dienes and alkynes has been investigated (M = Al, Zn, and Mg). Reaction of M·Zr with 1,5-cyclooctadiene led to diene isomerization to 1,3-cyclooctadiene, but for M = Zn also result in an on-metal diene-to-alkyne isomerization. The resulting cyclooctyne fragment is trapped between Zr and Zn metals in a heterobimetallic species that does not form for M = Mg or Al. The scope of diene isomerization and alkyne trapping has been explored leading to the isolation of three new heterobimetallic slipped metallocyclopropene complexes. The mechanism of diene-to-alkyne isomerization was investigated through kinetics. While the reaction is first-order in Zn·Zr at high diene concentration and proceeds with ΔH‡ = +33.6 ± 0.7 kcal mol–1, ΔS‡ = +23.2 ± 1.7 cal mol–1 K–1, and ΔG⧧298 K = +26.7 ± 1.2 kcal mol–1, the rate is dependent on the nature of the diene. The positive activation entropy is suggestive of involvement of a dissociative step. On the basis of DFT calculations, a heterobimetallic rebound mechanism for diene-to-alkyne isomerization has been proposed. This mechanism explains the origin of heterobimetallic control over selectivity: Mg---Zr complexes are too strongly bound to generate reactive fragments, while Al---Zr complexes are too weakly bound to compensate for the contrathermodynamic isomerization process. Zn---Zr complexes have favorable energetics for both dissociation and trapping steps." @default.
- W2788536055 created "2018-03-06" @default.
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- W2788536055 date "2018-02-28" @default.
- W2788536055 modified "2023-10-15" @default.
- W2788536055 title "Heterobimetallic Rebound: A Mechanism for Diene-to-Alkyne Isomerization with M---Zr Hydride Complexes (M = Al, Zn, and Mg)" @default.
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- W2788536055 doi "https://doi.org/10.1021/acs.organomet.7b00908" @default.
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