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Abstract: (Chemical Abstract 2008, : )
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Topological analyses of the electron density using the quantum theory of atoms in molecules (QTAIM) and
electron localization function (ELF) have been carried out, at the B3LYP/DGVZVP and MP2/DGVZVP
theoretical levels, on different 1,3-metalladiyne cyclic compounds [Cp2M(CCR)]2, (M = Ti, Zr; R = F, CH3,
H, SiH3). The QTAIM results indicate the presence of an extraordinarily long C-C bond (in a 2.7-3.0 Å
range) connecting the CCR moieties, contrary to the common geometrical assumption of a M-M bond in
similar metallacycles. The existence of this C-C bond is also supported by the distinct consequences on the
reaction profiles for the Ti and Zr complexes, the CC oxidative coupling reactions being favored only for the
Ti complexes. Moreover, the consequences of this bonding in the coupling/cleavage reactions of these
metallacyclic complexes are reported and analyzed, revealing the transcendence of these long-range bonds in
the overall behavior of these compounds.
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