アイテム詳細

要旨

Treatment of [MoCl₄(THF)₂] with MOtBu (M = Na, Li) does not result in simple metathetic ligand exchange but entails disproportionation with formation of the well-known dinuclear complex [(tBuO)₃Mo≡Mo(OtBu)₃] and a new paramagnetic compound, [Mo(OtBu)₅]. This particular five-coordinate species is the first monomeric, homoleptic, all-oxygen-ligated but non-oxo 4d¹ Mo(V) complex known to date; as such, it proves that the dominance of the Mo=O group over (high-valent) molybdenum chemistry can be challenged. [Mo(OtBu)₅] was characterized in detail by a combined experimental/computational approach using X-ray diffraction; UV/vis, MCD, IR, EPR, and NMR spectroscopy; and quantum chemistry. The recorded data confirm a Jahn–Teller distortion of the structure, as befitting a d¹ species, and show that the complex undergoes Berry pseudorotation. The alkoxide ligands render the disproportionation reaction, leading the formation of [Mo(OtBu)₅] to be particularly facile, even though the parent complex [MoCl₄(THF)₂] itself was also found to be intrinsically unstable; remarkably, this substrate converts into a crystalline material, in which the newly formed Mo(III) and Mo(V) products cohabitate the same unit cell.