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Ethylene Addition to Group‐9 Transition Metal Dioxo Compounds – A Quantum Chemical Study
Author(s) -
Haunschild Robin,
Frenking Gernot
Publication year - 2008
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200800243
Subject(s) - rhodium , transition metal , chemistry , iridium , cobalt , density functional theory , exothermic reaction , cycloaddition , metal , ethylene , quantum chemical , catalysis , photochemistry , inorganic chemistry , computational chemistry , molecule , organic chemistry
Quantum chemical calculations employing density functional theory (B3LYP) have been carried out to elucidate the reaction pathways for ethylene addition to iridium [IrO 2 CH 3 CH 2 ], rhodium [RhO 2 CH 3 CH 2 ] and cobalt [CoO 2 CH 3 CH 2 ] complexes. The comparison of the results shows that all three complexes prefer a [3+2] cycloaddition pathway rather than a [2+2] addition. For the iridium and rhodium species, the [3+2] C,O pathway where the transition metal‐carbon and transition metal‐oxygen double bonds are involved is favoured, whereas the cobalt compound prefers the [3+2] O,O addition where both transition metal‐oxygen double bonds are participating with concomitant hydrogen migration. For all three metal compounds, the reaction energies are highly exothermic and only small barriers are necessary to overcome.