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Ligand-promoted solvent-dependent ionization and conformational equilibria of Re(CO)Br[CH(S-tim)] (tim = 1-methylthioimidazolyl). Crystal structures of Re(CO)Br[CH (S-tim)] and {Re(CO)(CHCN) [CH(S-tim)]}(PF)

Inorganic Chemistry, ISSN: 0020-1669, Vol: 45, Issue: 17, Page: 6794-6802
2006
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  • Citations
    10
    • Citation Indexes
      10
  • Captures
    3

Article Description

The compounds Re(CO)Br[CH(S-tim)] (1) and {Re(CO)(CHCN)[CH(S-tim) ]}(PF) (2), where tim is 1-methyl-thioimidazolyl, were prepared in high yields and characterized both in the solid state and in solution. The solid-state structures show that the ligand acts in a chelating binding mode where the eight-member chelate ring adopts twist-boat conformations in both compounds. A comparison of both solid-state IR data for CO stretching frequencies and the solution-phase voltammetric measurements for the Re couples between 1, 2, and related N,N-chelates of the rhenium tricarbonyl moiety indicate that the CH(S-tim) ligand is a stronger donor than even the ubiquitous dipyridyl ligands. A combination of NMR spectroscopic studies and voltammetric studies revealed that compound 1 undergoes spontaneous ionization to form {Re(CO)(CH CN)[CH(S-tim)]}(Br) in acetonitrile. Ionization does not occur in solvents such as CH Cl or acetone that are less polar and Lewis basic (less coordinating). The equilibrium constant at 293 K for the ionization of 1 in CHCN is 4.3 × 10, The eight-member chelate rings in each 1 and 2 were found to be conformationally flexible in all solvents, and boat-chair conformers could be identified. Variable-temperature NMR spectroscopic studies were used to elucidate the various kinetic and thermodynamic parameters associated with the energetically accessible twist-boat to twist-boat and twist-boat to boat-chair interconversions. © 2006 American Chemical Society.

Bibliographic Details

Rosalice M. Silva; Brendan J. Liddle; Sergey J. Lindeman; James R. Gardinier; Mark D. Smith

American Chemical Society (ACS)

Chemistry

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