Molybdenum imidazole citrate and bipyridine homocitrate in different oxidation states – balance between coordinated α-hydroxy and α-alkoxy groups

Abstract

Oxo and thiomolybdenum(IV/VI) imidazole hydrocitrates K₂{Mo^IV₃O₄(im)₃[Mo^VIO₃(Hcit)]₂}·3im·4H₂O (1), (Him)₂{Mo^IV₃SO₃(im)₃[Mo^VIO₃(Hcit)]₂}·im·6H₂O (2), molybdenum(V) bipyridine homocitrate trans-[(Mo^VO)₂O(H₂homocit)₂(bpy)₂]·4H₂O (3) and molybdenum(VI) citrate (Et₄N)[Mo^VIO₂Cl(H₂cit)]·H₂O (4) (H₄cit = citric acid, H₄homocit = homocitric acid, im = imidazole and bpy = 2,2′-bipyridine) with different oxidation states were prepared. 1 and 2 are the coupling products of [Mo^VIO₃(Hcit)]³⁻ anions and incomplete cubane units [Mo^IV₃O₄]⁴⁺ ([Mo^IV₃SO₃]⁴⁺) with monodentate imidazoles, respectively, where tridentate citrates coordinate with α-hydroxy, α-carboxy and β-carboxy groups, forming pentanuclear skeleton structures. The molybdenum atoms in 1 and 2 show unusual +4 and +6 valences based on charge balances, theoretical bond valence calculations and Mo XPS spectrum. The coordinated citrates in 1 and 2 are protonated with α-hydroxy groups, while 3 and 4 with higher oxidation states of +5 and +6 are deprotonated with α-alkoxy group even under strong acidic condition, respectively. This shows the relationship between the oxidation state and protonation of the α-alkoxy group in citrate or homocitrate, which is related to the protonation state of homocitrate in FeMo-cofactor of nitrogenase. The homocitrate in 3 chelates to molybdenum(V) with bidentate α-alkoxy and monodentate α-carboxy groups. Molybdenum(VI) citrate 4 is only protonated with coordinated and uncoordinated β-carboxy groups. The solution behaviours of 1 and 2 are discussed based on ¹H and ¹³C NMR spectroscopies and cyclic voltammograms, showing no decomposition of the species.