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

摘要

(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((gamma-pic)2H)[Mo(NCS)4(gamma-pic)2](pic=picoline)with Br2 in air.The oxidation of((gamma-pic)2H)[Mo(NCS)4(gamma-pic)2]with a considerably lower concentration of Br2 in air gave(gamma-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 v(CN)and delta(NCS)bands indicate N-bonding of the NCS groups and are in agreement with the crystal-structure results.