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• W2108405136 abstract "The mechanisms of three closely related reactions were studied in detail by means of DFT/B3 LYP calculations with a VDZP basis set. Those reactions correspond to 1) the reductive elimination of methane from [Zr(eta5-Ind)2(CH3)(H)] (Ind=C9H7-, indenyl), 2) the formation of the THF adduct, [Zr(eta5-Ind)(eta6-Ind)(thf)] and 3) the interconversion between the two indenyl ligands in the Zr sandwich complex, [Zr(eta5-Ind)(eta9-Ind)], which forms the link between the two former reactions. An analysis of the electronic structure of this species indicates a saturated 18-electron complex. A full understanding of the indenyl interchange process required the characterisation of several isomers of the Zr-bis(indenyl) species, corresponding to different spin states (S=0 and S=1), different coordination modes of the two indenyl ligands (eta5/eta9, eta5/eta5 and eta6/eta9), and three conformations for each isomer (syn, anti, and gauche). The fluxionality observed was found to occur in a mechanism involving bis(eta5-Ind) intermediates, and the calculated activation energy (11-14 kcal mol(-1)) compares very well with the experimental values. Two alternative mechanisms were explored for the reductive elimination of methane from the methyl/hydride complex. In the more favourable one, the initial complex, [Zr(eta5-Ind)2(CH3)(H)], yields [Zr(eta5-Ind)2] and methane in one crucial step, followed by a smooth transition of the Zr intermediate to the more stable eta5/eta9-species. The overall activation energy calculated (Ea=29 kcal mol(-1)) compares well with experimental values for related species. The formation of the THF adduct follows a one step mechanism from the appropriate conformer of the [Zr(eta5-Ind)(eta9-Ind)] complex, producing easily (Ea=6.5 kcal mol(-1)) the known product, [Zr(eta5-Ind)(eta6-Ind)(thf)], a species previously characterised by X-ray crystallography. This complex was found to be trapped in a potential well that prevents it from evolving to the 3.4 kcal mol(-1) more stable isomer, [Zr(eta5-Ind)2(thf)], with both indenyl ligands in a eta5-coordination mode and a spin-triplet state (S=1)." @default.
• W2108405136 created "2016-06-24" @default.
• W2108405136 creator A5046772276 @default.
• W2108405136 date "2005-04-05" @default.
• W2108405136 modified "2023-10-16" @default.
• W2108405136 title "Zirconium Bis(indenyl) Sandwich Complexes with an Unprecedented Indenyl Coordination Mode and Their Role in the Reactivity of the Parent Bent-Metallocenes: A Detailed DFT Mechanistic Study" @default.
• W2108405136 cites W123872719 @default.
• W2108405136 cites W1964837435 @default.
• W2108405136 cites W1967320983 @default.
• W2108405136 cites W1967536443 @default.
• W2108405136 cites W1968974641 @default.
• W2108405136 cites W1971275758 @default.
• W2108405136 cites W1973443611 @default.
• W2108405136 cites W1974021462 @default.
• W2108405136 cites W1975708211 @default.
• W2108405136 cites W1975755749 @default.
• W2108405136 cites W1976625372 @default.
• W2108405136 cites W1978111198 @default.
• W2108405136 cites W1984599229 @default.
• W2108405136 cites W1984614201 @default.
• W2108405136 cites W1990442032 @default.
• W2108405136 cites W1993383767 @default.
• W2108405136 cites W1994457280 @default.
• W2108405136 cites W1997668513 @default.
• W2108405136 cites W1998509549 @default.
• W2108405136 cites W1998790035 @default.
• W2108405136 cites W2000487620 @default.
• W2108405136 cites W2002517524 @default.
• W2108405136 cites W2007843748 @default.
• W2108405136 cites W2011254772 @default.
• W2108405136 cites W2011984173 @default.
• W2108405136 cites W2013681136 @default.
• W2108405136 cites W2014091724 @default.
• W2108405136 cites W2015516088 @default.
• W2108405136 cites W2017794085 @default.
• W2108405136 cites W2020494564 @default.
• W2108405136 cites W2023271753 @default.
• W2108405136 cites W2032842297 @default.
• W2108405136 cites W2036217125 @default.
• W2108405136 cites W2038193875 @default.
• W2108405136 cites W2038767330 @default.
• W2108405136 cites W2041090462 @default.
• W2108405136 cites W2042619453 @default.
• W2108405136 cites W2042944554 @default.
• W2108405136 cites W2044490585 @default.
• W2108405136 cites W2046412723 @default.
• W2108405136 cites W2046789398 @default.
• W2108405136 cites W2051291379 @default.
• W2108405136 cites W2051403095 @default.
• W2108405136 cites W2058363175 @default.
• W2108405136 cites W2058850402 @default.
• W2108405136 cites W2061096233 @default.
• W2108405136 cites W2068617439 @default.
• W2108405136 cites W2075381847 @default.
• W2108405136 cites W2075662351 @default.
• W2108405136 cites W2077041472 @default.
• W2108405136 cites W2078464425 @default.
• W2108405136 cites W2083062412 @default.
• W2108405136 cites W2084876683 @default.
• W2108405136 cites W2085966856 @default.
• W2108405136 cites W2086288648 @default.
• W2108405136 cites W2093433105 @default.
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• W2108405136 cites W2099308235 @default.
• W2108405136 cites W2113149303 @default.
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• W2108405136 cites W2143084823 @default.
• W2108405136 cites W2143981217 @default.
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• W2108405136 cites W2166221263 @default.
• W2108405136 cites W2217610646 @default.
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• W2108405136 doi "https://doi.org/10.1002/chem.200401235" @default.
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