Abstract
The electronic and geometrical structures of a variety of LmMn−C2 organometallic systems (n ≥ 5) in which the dicarbon unit is solely bonded to metal atoms are analyzed and compared by use of molecular orbital calculations. It is shown that the arrangement of the M5 and M6 cores can be derived from a square-pyramidal and a trigonal-prismatic geometry, respectively. The bonding of the C2 ligand with its metallic host follows the Dewar-Chatt-Duncanson model, resulting from an important forward electron donation from occupied C2 orbitals toward acceptor metallic orbitals, accompanied by a back-donation from occupied metallic orbitals into vacant C2 π* orbitals.
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