Delocalized and localized donating-accepting Mn-C interactions in half-sandwich cyclopentadienyl and pentadienyl complexes
Por:
Solis-Huitron, Josue, Zuniga-Villarreal, Noe, Martinez-Otero, Diego, Enrique Barquera-Lozada, Jose
Publicada:
7 jun 2017
Categoría:
Inorganic chemistry
Resumen:
The widely used cyclopentadienyl (Cp) ligand and the pentadienyl (Pdl)
ligand have very similar molecular orbitals (MOs) but they have
significantly different chemical behavior. The extensively mixing of the
MOs in the Pdl ligand has prevented a quantitative explanation of the
observed differences between these two ligands. In a series of
synthesized close/open half sandwich manganese phosphine carbonyls, the
quantum theory of atoms in molecules and the interacting quantum atom
model allow us to quantify the accepting-donating capacities of both
ligands and to break down the M-dienyl bond into individual atomic
interactions. The Mn-Pdl bond is stronger, more localized and has a
larger backbonding contribution than the Mn-Cp bond. All carbon atoms in
the Cp ring interact similarly with the Mn center, whereas the Pdl's
terminal carbon atoms exhibit a strong donor and a moderate acceptor
character, and C2 and C4 have an acceptor character and C3 a donor
character. Contrarily to the constrained five-membered Cp ring, the
stronger Mn-Pdl interaction can barely compensate for the large
destabilizing distortion of the backbone of the nonaromatic Pdl ligand.
Filiaciones:
Solis-Huitron, Josue:
Univ Nacl Autonoma Mexico, Chem Inst, Ciudad De Mexico, Mexico
Zuniga-Villarreal, Noe:
Univ Nacl Autonoma Mexico, Chem Inst, Ciudad De Mexico, Mexico
Martinez-Otero, Diego:
Ctr Conjunto Invest Quim Sustentable UAEM UNAM Ca, Toluca Atlacomunco Km 14-5, Toluca 50200, Edo Mex, Mexico
Enrique Barquera-Lozada, Jose:
Univ Nacl Autonoma Mexico, Chem Inst, Ciudad De Mexico, Mexico
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