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The synthesis of <jats:bold>1<\/jats:bold> is facile (20\u2009\u00b0C, overnight), but generation of decamethylberyllocene <jats:bold>2<\/jats:bold> demands high temperatures (ca. 115\u2009\u00b0C) and extended reaction times (3\u20134 days). The mixed\u2010ring beryllocene <jats:bold>3<\/jats:bold> is obtained when the known [(<jats:italic>\u03b7<\/jats:italic><jats:sup>5<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>Me<jats:sub>5<\/jats:sub>)BeCl] is allowed to react with K[C<jats:sub>5<\/jats:sub>Me<jats:sub>4<\/jats:sub>H], once more under somewhat forcing conditions (115\u2009\u00b0C, 36 h). The structures of the three metallocenes have been determined by low\u2010temperature X\u2010ray studies. Both <jats:bold>1<\/jats:bold> and <jats:bold>3<\/jats:bold> present <jats:italic>\u03b7<\/jats:italic><jats:sup>5<\/jats:sup>\/<jats:italic>\u03b7<\/jats:italic><jats:sup>1<\/jats:sup> geometries of the slip\u2010sandwich type, whereas <jats:bold>2<\/jats:bold> exhibits an almost regular, ferrocene\u2010like, sandwich structure. In the mixed\u2010ring compound <jats:bold>3<\/jats:bold>, C<jats:sub>5<\/jats:sub>Me<jats:sub>5<\/jats:sub> is centrally bound to beryllium and the <jats:italic>\u03b7<\/jats:italic><jats:sup>1<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>Me<jats:sub>4<\/jats:sub>H ring bonds to the metal through the unique CH carbon atom. This is also the binding mode of the <jats:italic>\u03b7<\/jats:italic><jats:sup>1<\/jats:sup>\u2010ring of <jats:bold>1<\/jats:bold>. To analyze the nature of the bonding in these molecules, theoretical calculations at different levels of theory have been performed on compounds <jats:bold>2<\/jats:bold> and <jats:bold>3<\/jats:bold>, and a comparison with the bonding in [Be(C<jats:sub>5<\/jats:sub>H<jats:sub>5<\/jats:sub>)<jats:sub>2<\/jats:sub>] has been made. As for the latter molecule, energy differences between the <jats:italic>\u03b7<\/jats:italic><jats:sup>5<\/jats:sup>\/<jats:italic>\u03b7<\/jats:italic><jats:sup>5<\/jats:sup> and the <jats:italic>\u03b7<\/jats:italic><jats:sup>5<\/jats:sup>\/<jats:italic>\u03b7<\/jats:italic><jats:sup>1<\/jats:sup> structures of <jats:bold>2<\/jats:bold> are very small, being of the order of a few kcal\u2009mol<jats:sup>\u22121<\/jats:sup>. Constrained space orbital variations (CSOV) calculations show that the covalent character in the bonding is larger for [Be(C<jats:sub>5<\/jats:sub>Me<jats:sub>5<\/jats:sub>)<jats:sub>2<\/jats:sub>] than for [Be(C<jats:sub>5<\/jats:sub>H<jats:sub>5<\/jats:sub>)<jats:sub>2<\/jats:sub>] due to larger charge delocalization and to increased polarizability of the C<jats:sub>5<\/jats:sub>Me<jats:sub>5<\/jats:sub> fragment.<\/jats:p>","DOI":"10.1002\/chem.200304876","type":"journal-article","created":{"date-parts":[[2003,9,17]],"date-time":"2003-09-17T10:19:45Z","timestamp":1063793985000},"page":"4452-4461","source":"Crossref","is-referenced-by-count":40,"title":["Synthesis, Solid\u2010State Structure, and Bonding Analysis of the Beryllocenes [Be(C<sub>5<\/sub>Me<sub>4<\/sub>H)<sub>2<\/sub>], [Be(C<sub>5<\/sub>Me<sub>5<\/sub>)<sub>2<\/sub>], and [Be(C<sub>5<\/sub>Me<sub>5<\/sub>)(C<sub>5<\/sub>Me<sub>4<\/sub>H)]"],"prefix":"10.1002","volume":"9","author":[{"given":"M.","family":"del Mar Conejo","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Rafael","family":"Fern\u00e1ndez","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Diego","family":"del\u2009R\u00edo","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ernesto","family":"Carmona","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Angeles","family":"Monge","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Caridad","family":"Ruiz","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Antonio M.","family":"M\u00e1rquez","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Javier","family":"Fern\u00e1ndez\u2009Sanz","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2003,9,11]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/om020168o"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr941099t"},{"key":"e_1_2_6_4_2","volume-title":"Metallocenes Vol. 1","author":"Jutzi P.","year":"1998"},{"key":"e_1_2_6_5_2","volume-title":"Comprehensive Organometallic Chemistry II, Vol. 1","author":"Bell N. 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