Synthesis and Characterization of TpiPrMoO(S2PR2) (R = Pri, Ph, OEt, OPri, (−)-Mentholate) and {HB(OMe)(Pripz)2}MoO(S2PPri2), Including Isomers of Known 1,2-Borotropically-Shifted Complexes Academic Article uri icon

abstract

  • Green/blue TpiPrMoO(S2PR2) (TpiPr = hydrotris(3-isopropylpyrazolyl)borate; R = Pri, Ph, OEt, OPri, (-)-mentholate) complexes were synthesized and characterized by elemental analysis, mass spectrometry, IR and NMR spectroscopy, and X-ray crystallography. The diamagnetic, six-coordinate, oxo-Mo(IV) complexes possess distorted octahedral geometries defined by terminal oxo, bidentate dithio acid, and tridentate TpiPr ligands. The R = Pri and Ph derivatives are isomers of previously reported 1,2-borotropically shifted complexes, TpiPr*MoO(S2PR2) (TpiPr* = hydrobis(3-isopropylpyrazolyl)(5-isopropylpyrazolyl)borate; ref: Inorg. Chem. 1996, 35, 5368). Conversion of TpiPrMoO(S2PPh2) into TpiPr*MoO(S2PPh2) at elevated temperatures (>80 degrees C) showed that the borotropically shifted isomer was thermodynamically more stable than the unshifted species. Reaction with methanol converts TpiPrMoO(S2PPri2) into {HB(OMe)(Pripz)2}MoO(S2PPri2) (Pripz = 3-isopropylpyrazolyl), which was characterized by spectroscopic and crystallographic methods.

authors

  • Young, Charles G
  • Malarek, Michael S
  • Evans, David J
  • Doonan, Christian J
  • Ng, Victor Wee Lin
  • White, Jonathan M

publication date

  • March 2, 2009