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

Abstract

The 1 : 1 reaction of MoCl₅ with 1,4-Me(SO₃Me)C₆H₄ led to the isolation of crystalline Mo₂O₂Cl₆[μ–κ²-1,4-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(μ-Cl)(κ¹-1,4-Me(SO₃Me)C₆H₄)]₂, 2. The 1 : 1 reaction of MoCl₅ with 1,4-Me(SO₃H)C₆H₄·H₂O selectively yielded Mo₄O₄Cl₈[μ₃-1,4-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.