Nonclassical vs classical metal center dot center dot center dot H3C-C interactions: Accurate characterization of a 14-electron Ruthenium(II) system by neutron diffraction, database analysis, solution dynamics, and DFT studies (Articolo in rivista)

Type
Label
  • Nonclassical vs classical metal center dot center dot center dot H3C-C interactions: Accurate characterization of a 14-electron Ruthenium(II) system by neutron diffraction, database analysis, solution dynamics, and DFT studies (Articolo in rivista) (literal)
Anno
  • 2004-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/ja038986a (literal)
Alternative label
  • Baratta, Walter; Mealli, Carlo; Herdtweck, Eberhardt; Ienco, Andrea; Mason, Sax A.; Rigo, Pierluigi (2004)
    Nonclassical vs classical metal center dot center dot center dot H3C-C interactions: Accurate characterization of a 14-electron Ruthenium(II) system by neutron diffraction, database analysis, solution dynamics, and DFT studies
    in Journal of the American Chemical Society (Print); ACS, American chemical society, Washington, DC (Stati Uniti d'America)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Baratta, Walter; Mealli, Carlo; Herdtweck, Eberhardt; Ienco, Andrea; Mason, Sax A.; Rigo, Pierluigi (literal)
Pagina inizio
  • 5549 (literal)
Pagina fine
  • 5562 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#url
  • http://pubs.acs.org/doi/abs/10.1021/ja038986a (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 126 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#pagineTotali
  • 14 (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Dipartimento di Scienze e Tecnologie Chimiche, Università di Udine, Via Cotonificio 108, I-33100 Udine, Italy; Istituto di Chimica dei Composti Organometallici (ICCOM-CNR), Via Madonna del Piano, I-50019 Sesto Fiorentino (Firenze), Italy; Anorganisch-chemisches Institut, Technische Universität München, Lichtenbergstrasse 4, D-85747 Garching, Germany; Institut Max von Laue-Paul Langevin, 6, Rue Jules Horowitz, BP 156, F-38042 Grenoble Cedex 9, France (literal)
Titolo
  • Nonclassical vs classical metal center dot center dot center dot H3C-C interactions: Accurate characterization of a 14-electron Ruthenium(II) system by neutron diffraction, database analysis, solution dynamics, and DFT studies (literal)
Abstract
  • A neutron diffraction study of the complex RuCl2[PPh2(2,6-Me2C6H3)](2) (1) defines the precise nature of the delta agostic interactions between the unsaturated metal center and two o-methyl groups of the xylyl substituents. The CH3 carbon atoms lie in the RuP2 equatorial plane with Ru...C distances of 2.637(7) and 2.668(6) Angstrom, whereas four short Ru...H distances (from 2.113(11) to 2.507(11) Angstrom) indicate that each methyl group interacts with two C-H bonds. A survey of the X-ray structures with beta, gamma, delta, and epsilon M...H3C-C moieties (no neutron data have been previously reported) shows a linear correlation between the angle M...C-C and the torsion of the methyl group about the C-C bond. Thus, the agostic interactions span the range between the classical (M...eta(2)-HC) and the nonclassical (M...eta(3)-H2C) types. A solution study of 1 shows intramolecular rearrangement of each xylyl substituent that equilibrates the environments of its two ortho CH3 groups. Activation parameters, evaluated from the analysis of H-1 NMR line shape as a function of temperature, are DeltaH(double dagger) = 9.6 +/- 0.2 kcal mol(-1) with DeltaS(double dagger) = -15.4 +/- 0.7 eu (CDCl3). The related 14-electron complexes RuX2[PPh2(2,6-Me2C6H3)](2) (X = I, 2; NCO, 3), prepared from 1 and NaX, show a similar dynamic process in solution, with the iodo derivative displaying the most hindered rotation of the xylyl group. A DFT optimization of the complex RuCl2[PH2(2,6-Me2C6H3)](2) (1a) reproduces well the nonclassical Ru...eta(3)-H2C agostic mode, whereas the classical Ru...eta(2)-HC one corresponds to a transition state 1b, destabilized by 3.4 kcal mol(-1). A similar barrier (ca. 3.8 kcal mol(-1)) is calculated for the xylyl rotation in the further simplified model RuCl2[PH2(2,6-Me2C6H3)][PH2CH=CHCH3] (1c), the absence of bulky phenyl substituents; being largely responsible for the difference with respect to the experimental value. Finally, the MO analysis addresses the intrinsic stability of the 14-electron complex RuCl2(PH3)(2) and, in agostic complexes, accounts for the different interactions between the methyl group and the metal atom in relation to the length of their interconnecting chain. (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