A counterintuitive structural effect of metal-metal bond protonation and its electronic underpinnings (Articolo in rivista)

Type
Label
  • A counterintuitive structural effect of metal-metal bond protonation and its electronic underpinnings (Articolo in rivista) (literal)
Anno
  • 2006-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1002/chem.200501071 (literal)
Alternative label
  • Phillips, Andrew D.; Ienco, Andrea; Reinhold, Joachim; Boettcher, Hans-Christian; Mealli, Carlo (2006)
    A counterintuitive structural effect of metal-metal bond protonation and its electronic underpinnings
    in Chemistry (Weinh., Print); WILEY-V C H VERLAG GMBH, WEINHEIM (Germania)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Phillips, Andrew D.; Ienco, Andrea; Reinhold, Joachim; Boettcher, Hans-Christian; Mealli, Carlo (literal)
Pagina inizio
  • 4691 (literal)
Pagina fine
  • 4701 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 12 (literal)
Rivista
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • CNR, ICCOM, I-50019 Sesto Fiorentino, Firenze, Italy Univ Leipzig, Wilhlem Ostwald Inst Phys & Theoret Chem, D-04103 Leipzig, Germany Univ Munich, Dept Chem & Biochem, D-81377 Munich, Germany (literal)
Titolo
  • A counterintuitive structural effect of metal-metal bond protonation and its electronic underpinnings (literal)
Abstract
  • Protonation across the metal-metal bond in the complexes [(CO)(2)M(mu-dppm)(mu-PtBu2)(mu-H)-M(CO)(2)] (M=Fe or Ru, dppm= Ph2PCH2PPh2) induces M-M bond shortening of up to about 0.05 angstrom. DFT calculations on simplified iron models reproduce this trend well. Conversely, the computations show that the M-M distance in the dimer [{Cp*Ir(CO)}(2)] lengthens with two consecutive protonations, but there are no crystal structure determinations to highlight the effects on the Ir-Ir bond. DFT calculations and the analogous cobalt system confirm that the transformation of a two-electron, two-center (2e-2c) bond into a 2e-3c bond is accompanied by the predicted elongation. An MO analysis indicated similar nature and evolution of the M-M bonding these cases. In particular, the HOMOs of the mono-hydrido cations [Cp(CO)M(mu-H)M(CO)Cp](+) (M=Ir, Co) have evident M-M bent-bond character, and hence subsequent protonation invariably causes a decrease in the bond index. The Fe2 and Co2 systems have also been analyzed with the quantum theory of atoms. in molecules (QTAIM) method, but in no case was an M-M bond critical point located unless an artificially shorter M-M distance was imposed. However, the trends for the atoms-in-molecules (AIM) bond delocalization indexes delta(M)-(M) confirm the overall M-M bond weakening on protonation. In conclusion, all the computational results for the iron system indicate that the paradigm of a direct correlation between bond strength and distance is not always applicable. This is attributable to a very flat potential energy surface and various competing effects imposed by the bridging ligands. (literal)
Editore
Prodotto di
Autore CNR

Incoming links:


Prodotto
Autore CNR di
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#rivistaDi
Editore di
data.CNR.it