Synthesis of di- and tetranuclear oxidomolybdenum(V) complexes containing p-toluenesulfonates as ligands: a joint spectroscopic, crystallographic and computational study

The 1 : 1 reaction of MoCl5 with 1,4-Me(SO3Me) C6H4 led to the isolation of crystalline Mo2O2Cl6[mu-k(2)-1,4- Me(SO3Me) C6H4], 1, in low yields. Attempts to reproduce the synthesis of 1 from MoOCl3/ 1,4-Me (SO3Me) C6H4 resulted in the good-yield formation of [MoOCl2(mu-Cl)(k(1)-1,4-Me(SO3Me) C6H4)](2),2. The 1 : 1 reaction of MoCl5 with 1,4-Me(SO3H) C6H4 center dot H2O selectively yielded Mo4O4Cl8[mu(3)-1,4-Me(SO3) C6H4](4), 3. Compounds 1 and 3 were characterized by X-ray diffractometry; moreover DFT calculations were carried out on 1-3 in order to shed light on their thermodynamic and structural features.