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Abstract: (Chemical Abstract 2005, : )
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Ab initio and DFT calculations have been performed on a series of organometallic compounds, according to the formula MCHn, where M = K, Ca, Sc, Ti, V, Cr, or Mn and n = 1-3. Various theoretical methods are compared, the B3LYP level yielding the same agreement with the experimental geometries available as the correlated MP2
and CISD methods, with the 6-311++G(3df,2p) basis set for C,H and Wachter's (15s11p6d3f1g)/[10s7p4d3f1g], basis set for transition metals. The main geometric and electronic features of the molecules studied are described, analyzing the M-C bonding characteristics in terms of the atoms in molecules theory (AIM) and the electron localization function (ELF). Although multiple bonding is expected from the Lewis bonding scheme, the results indicate an almost pure ionic bond for all the systems studied. The net charge transfer from the metal to the carbon atom ranges from 0.5 to 1 e-, and the electronic structure of the CHn- moiety is unaltered after the interaction with the metal cation, showing little or no effect on the shape of the electron pairing.
The bond paths corresponding to a possible α-agostic bond for these systems are not present.
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