Synthesis And Characterization of Mo(V)-oxido Complexes Containing the Thiocyanato-N Ligand

Nives Kitanovski,* Amalija Golobič and Boris Čeh

University of Ljubljana, Faculty of Chemistry and Chemical Technology, Aškerčeva 5, 1001 Ljubljana, Slovenia.
* Corresponding author: E-mail:

(P(C6H5)4)2[MoO(NCS)5] (1) crystallized after addition of (P(C6H5)4)Br to the mixture obtained by refluxing (pyH)5[MoOCl4(H2O)]3Cl2 (py = pyridine) and KSCN in acetonitrile, and also by oxidation of (( γ-pic)2H)[Mo(NCS)4 ( γ-pic)2] (pic = picoline) with Br2 in air. The oxidation of (( γ-pic)2H)[Mo(NCS)4( γ-pic)2] with a considerably lower concentration of Br2 in air gave ( γ-picH)6[Mo2O3(SO4)(NCS)6](SO4) (2). (pyH)8[Mo2O3(NCS)8]X4 (X = Br, 3; X = Cl, 4) were isolated after addition of pyHX to the hydrolysis product of [MoO(NCS)5]2–. The compounds were characterized by IR spectroscopy and single crystal X-ray diffraction analysis. The positions of the ν(CN) and δ(NCS) bands indicate N-bonding of the NCS groups and are in agreement with the crystal-structure results.

Keywords: Molybdenum(V), thiocyanato-N, crystal structures.