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.
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.
Young
Charles G
CG
School of Chemistry, University of Melbourne, Victoria 3010, Australia. cgyoung@unimelb.edu.au
Malarek
Michael S
MS
Evans
David J
DJ
Doonan
Christian J
CJ
Ng
Victor Wee Lin
VW
White
Jonathan M
JM
D001895:Boron / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007536:Isomerism; D000432:Methanol / Q000737:chemistry; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013057:Spectrum Analysis
D009942:Organometallic Compounds; D008982:Molybdenum; D001895:Boron; D000432:Methanol