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Those reactions correspond to 1) the reductive elimination of methane from [Zr(\u03b7<jats:sup>5<\/jats:sup>\u2010Ind)<jats:sub>2<\/jats:sub>(CH<jats:sub>3<\/jats:sub>)(H)] (Ind=C<jats:sub>9<\/jats:sub>H<jats:sub>7<\/jats:sub><jats:sup>\u2212<\/jats:sup>, indenyl), 2) the formation of the THF adduct, [Zr(\u03b7<jats:sup>5<\/jats:sup>\u2010Ind)(\u03b7<jats:sup>6<\/jats:sup>\u2010Ind)(thf)] and 3) the interconversion between the two indenyl ligands in the Zr sandwich complex, [Zr(\u03b7<jats:sup>5<\/jats:sup>\u2010Ind)(\u03b7<jats:sup>9<\/jats:sup>\u2010Ind)], which forms the link between the two former reactions. An analysis of the electronic structure of this species indicates a saturated 18\u2010electron complex. A full understanding of the indenyl interchange process required the characterisation of several isomers of the Zr\u2013bis(indenyl) species, corresponding to different spin states (<jats:italic>S<\/jats:italic>=0 and <jats:italic>S<\/jats:italic>=1), different coordination modes of the two indenyl ligands (\u03b7<jats:sup>5<\/jats:sup>\/\u03b7<jats:sup>9<\/jats:sup>, \u03b7<jats:sup>5<\/jats:sup>\/\u03b7<jats:sup>5<\/jats:sup> and \u03b7<jats:sup>6<\/jats:sup>\/\u03b7<jats:sup>9<\/jats:sup>), and three conformations for each isomer (<jats:italic>syn<\/jats:italic>, <jats:italic>anti<\/jats:italic>, and <jats:italic>gauche<\/jats:italic>). The fluxionality observed was found to occur in a mechanism involving bis(\u03b7<jats:sup>5<\/jats:sup>\u2010Ind) intermediates, and the calculated activation energy (11\u201314 kcal\u2009mol<jats:sup>\u22121<\/jats:sup>) 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(\u03b7<jats:sup>5<\/jats:sup>\u2010Ind)<jats:sub>2<\/jats:sub>(CH<jats:sub>3<\/jats:sub>)(H)], yields [Zr(\u03b7<jats:sup>5<\/jats:sup>\u2010Ind)<jats:sub>2<\/jats:sub>] and methane in one crucial step, followed by a smooth transition of the Zr intermediate to the more stable \u03b7<jats:sup>5<\/jats:sup>\/\u03b7<jats:sup>9<\/jats:sup>\u2010species. The overall activation energy calculated (<jats:italic>E<\/jats:italic><jats:sub>a<\/jats:sub>=29 kcal\u2009mol<jats:sup>\u22121<\/jats:sup>) 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(\u03b7<jats:sup>5<\/jats:sup>\u2010Ind)(\u03b7<jats:sup>9<\/jats:sup>\u2010Ind)] complex, producing easily (<jats:italic>E<\/jats:italic><jats:sub>a<\/jats:sub>=6.5 kcal\u2009mol<jats:sup>\u22121<\/jats:sup>) the known product, [Zr(\u03b7<jats:sup>5<\/jats:sup>\u2010Ind)(\u03b7<jats:sup>6<\/jats:sup>\u2010Ind)(thf)], a species previously characterised by X\u2010ray crystallography. This complex was found to be trapped in a potential well that prevents it from evolving to the 3.4 kcal\u2009mol<jats:sup>\u22121<\/jats:sup> more stable isomer, [Zr(\u03b7<jats:sup>5<\/jats:sup>\u2010Ind)<jats:sub>2<\/jats:sub>(thf)], with both indenyl ligands in a \u03b7<jats:sup>5<\/jats:sup>\u2010coordination mode and a spin\u2010triplet state (<jats:italic>S<\/jats:italic>=1).<\/jats:p>","DOI":"10.1002\/chem.200401235","type":"journal-article","created":{"date-parts":[[2005,2,24]],"date-time":"2005-02-24T06:54:20Z","timestamp":1109228060000},"page":"2505-2518","source":"Crossref","is-referenced-by-count":32,"title":["Zirconium Bis(indenyl) Sandwich Complexes with an Unprecedented Indenyl Coordination Mode and Their Role in the Reactivity of the Parent Bent\u2010Metallocenes: A Detailed DFT Mechanistic Study"],"prefix":"10.1002","volume":"11","author":[{"given":"Luis F.","family":"Veiros","sequence":"first","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2005,4,5]]},"reference":[{"journal-title":"The Organometallic Chemistry of the Transition Metals","first-page":"3rd","author":"Crabtree R. 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They can be obtained from a natural population analysis and provide an indication on the bond strength."},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19971091612"},{"key":"e_1_2_6_28_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199717141"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00349a004"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1039\/a805682j"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19821151009"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1039\/a908532g"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1039\/a827263z"},{"key":"e_1_2_6_34_2","unstructured":"\u00a0"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1016\/0166-1280(88)80248-3"},{"key":"e_1_2_6_36_2","unstructured":"J. E. Carpenter Ph.D. thesis University of Wisconsin (Madison WI) 1987;"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00544a007"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.445134"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.445134"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.449486"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00088a005"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4684-7424-4_24"},{"key":"e_1_2_6_43_2","unstructured":"For excellent reviews on MECP and their location for transition\u2010metal complexes see:"},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(02)00283-7"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1039\/b200675h"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108768102003890"},{"key":"e_1_2_6_47_2","unstructured":"\u00a0"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50150a003"},{"key":"e_1_2_6_49_2","unstructured":"The structure optimised for [Zr(\u03b75\u2010Ind)2(Me)(H)] compares also very well with the X\u2010ray structure of [Zr(\u03b75\u2010Ind\u2032)(\u03b75\u2010Ind\u2032\u2032)(iPr)(H)] with substituted indenyls Ind\u2032=C9H6tBu Ind\u2032\u2032=C9H5(SiMe3)2(P. J. Chirik unpublished results). The experimental distances for the Zr\uf8ffC(indenyl) bonds are within 0.07 \u00c5 of the calculated values the corresponding differences being 0.02 \u00c5 for the ancillary ligands Zr\uf8ffC(iPr) and Zr\uf8ffH. The calculated L\u2010Zr\u2010L angles are within 2\u00b0 of the experimental ones."},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1039\/b111257k"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00193a022"},{"key":"e_1_2_6_52_2","unstructured":"In the case of the Zr complex the reductive elimination of alkane is followed by oxidative addition of a C\uf8ffH bond of one of the Cp\u2032 substituents yielding a cyclometalated product (see ref. [11]). The agreement between calculated and experimental activation parameters suggests that alkane elimination is the rate\u2010determining step."},{"key":"e_1_2_6_53_2","unstructured":"P. J. 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