Napredna pretraga

Pregled bibliografske jedinice broj: 544349

Fluxionality of Hydrogen Ligands in Fe(H)(2)(H(2))(PEtPh(2))(3))

Došlić, Nadja; Gomzi, Vjeran; Mališ, Momir; Matanović, Ivana; Eckert, Juergen
Fluxionality of Hydrogen Ligands in Fe(H)(2)(H(2))(PEtPh(2))(3)) // Inorganic chemistry, 50 (2011), 21; 10740-10747 doi:10.1021/ic201248z (međunarodna recenzija, članak, znanstveni)

Fluxionality of Hydrogen Ligands in Fe(H)(2)(H(2))(PEtPh(2))(3))
(Fluxionality of Hydrogen Ligands in Fe(H)(2)(H(2))(PEtPh(2))(3))

Došlić, Nadja ; Gomzi, Vjeran ; Mališ, Momir ; Matanović, Ivana ; Eckert, Juergen

Inorganic chemistry (1520-510X) 50 (2011), 21; 10740-10747

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Fluxionality; hydrogen storage

Extensive computational investigations along with additional quasielastic neutron scattering data were used to obtain a consistent picture of the extensive fluxionality of hydride and dihydrogen ligands in Fe(H)(2)(H(2))(PEtPh(2))(3) over a wide range of temperatures from 1.5 to 320 K. We were able to identify three different regimes in the dynamical processes based on activation energies obtained from line spectral broadening. The rotational tunneling lines (coherent exchange of the two hydrogens of the H(2) ligand) are broadened with increasing temperature by incoherent exchange up to about 80 K at which point they merge into a quasielastic spectrum from 100 K to about 225 K. The effective activation energies for the two regions are 0.14 and 0.1 kcal mol(-1), respectively. A third dynamical process with a higher activation energy of 0.44 kcal mol(-1) dominates above 225 K, which we attribute to a quantum dynamical exchange of dihydrogen and hydride ligands. Our detailed density functional theory (DFT) structural calculations involving the three functionals (B3LYP, TPSS, and wB97XD) provide a good account of the experimental structure and rotational barriers when only the hydrogen ligands are relaxed. Full relaxation of the "gas-phase" molecule, however, appears to occur to a greater degree than what is possible in the crystal structure. The classical dihydrogen-hydride exchange path involves a cis-dihydrogen and tetrahydride structure with energies of 6.49 and 7.38 kcal mol(-1), respectively. Experimental observation of this process with much lower energies would seem to suggest involvement of translational tunneling in addition to the rotational tunneling. Dynamics of this type may be presumed to be important in hydrogen spillover from metal particles, and therefore need to be elucidated in an effort to utilize this phenomenon.

Izvorni jezik

Znanstvena područja


Projekt / tema
098-0352851-2921 - Kontrola atomske i molekulske dinamike oblikovanim elektromagnetskim poljima (Nađa Došlić, )

Institut "Ruđer Bošković", Zagreb

Časopis indeksira:

  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus