Synthesis and Characterization of Tp<sup><i>i</i>Pr</sup>MoO(S<sub>2</sub>PR<sub>2</sub>) (R = Pr<sup><i>i</i></sup>, Ph, OEt, OPr<sup><i>i</i></sup>, (−)-Mentholate) and {HB(OMe)(Pr<sup><i>i</i></sup>pz)<sub>2</sub>}MoO(S<sub>2</sub>PPr<sup><i>i</i></sup><sub>2</sub>), Including Isomers of Known 1
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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 °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.
