`Half-Bonds' in an Unusual Coordinated S-4(2-) Rectangle (Articolo in rivista)

Type
Label
  • `Half-Bonds' in an Unusual Coordinated S-4(2-) Rectangle (Articolo in rivista) (literal)
Anno
  • 2009-01-01T00:00:00+01:00 (literal)
Alternative label
  • Poduska, Anne; Hoffmann, Roald; Ienco, Andrea; Mealli, Carlo (2009)
    `Half-Bonds' in an Unusual Coordinated S-4(2-) Rectangle
    in Chemistry - an Asian journal (Print)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Poduska, Anne; Hoffmann, Roald; Ienco, Andrea; Mealli, Carlo (literal)
Pagina inizio
  • 302 (literal)
Pagina fine
  • 313 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 4 (literal)
Rivista
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14850 (USA) Istituto di Chimica dei Composti Organometallici, ICCOM-CNR, Via Madonna del Piano 10, 50019 Sesto Fiorentino, Firenze (Italy) (literal)
Titolo
  • `Half-Bonds' in an Unusual Coordinated S-4(2-) Rectangle (literal)
Abstract
  • The bonding of a rare S42? rectangle coordinated to four transition metals (synthesized by Isobe, Nishioka, and co-workers), [{M2(h5-C5Me5)2(m-CH2)2}2(m-S4)]2+ (M=Rh, Ir) is analyzed. DFT calculations indicate that, while experiment gives the rectangle coordinated with its long edge parallel to Rh?Rh bonds and perpendicular to the Ir?Ir bonds, either orientation is feasible for both metals. Although rotation of the S4 rectangle is likely a multi-step process, a calculated barrier of 46 kcalmol?1 for a simple interconversion pathway goes through a trapezoidal, not a square, transition state. An argument is presented, based on molecular orbital (MO) calculations, that the long S?S contacts (2.70 and 2.90 ?) in the rectangle are in fact two center, three-electron bonds (or \"halfbonds\"). Moreover, the 2? charge on the S4 rectangle is related to a Jahn-Teller distortion from a square to a rectangle. Finally, DFT is used to explore possible stable intermediates in the oxidative process giving these M4S4 2+ compounds: for Ir, the coupling of two Ir2S2 + molecules appears feasible, as opposed to a possible two-electron oxidation of a neutral Rh4S4 molecule. (literal)
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