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
ISSN: 14779226
Editorial
ROYAL SOC CHEMISTRY, THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND, Reino Unido
Tipo de documento: Article
Volumen: 46 Número: 21
Páginas: 6958-6967
WOS Id: 000402550500016
ID de PubMed: 28513726