Structural and magnetic characterization of mixed-valence vanadium (IV/V) complex with {(VO)2(µ‒O)}3+ core: Theoretical and experimental insights

Regioselectivity of concerted proton–electron transfer at the surface of a polyoxovanadate cluster

“…Additional evidence for localization of electron density across the [V 2 O 3 ] 3+ regime in this framework can be obtained by comparing the UV-vis/NIR spectrum of 2-V 6 O 8 2− to other [V 2 O 3 ] 3+ -containing complexes in the literature. 40,41 Mixed-valent dimeric species feature a broad absorption band beginning at 750 nm and stretching beyond 1000 nm in analogy the observed spectrum for 2-V 6 O 8 2− .…”

“…The lack of additional equivalent vanadate units in 2-V 6 O 8 2− further limits electron shuttling beyond the two μ 2 -oxide-bound V centres, rendering its electronic structure more similar to the ligand-supported oxide-bridged V dimers described above. 40,41…”

“…Such asymmetry in the solid state is consistent with previously reported V IV/V mixed-valent vanadium-oxo dimers which feature similarly differentiated V-O b bond lengths on either side of the m 2 -O 2− ligand. 40,41 Indeed, these works describe V 2 O 3 subunits supported by multidentate ligands, and have been shown to feature D V-Ob values as high as 0.2 Å resulting from localization of V IV and V V in the solid phase at low temperature. 40 vanadate units in 2-V 6 O 8 2− further limits electron shuttling beyond the two m 2 -oxide-bound V centres, rendering its electronic structure more similar to the ligand-supported oxidebridged V dimers described above.…”

“…40 vanadate units in 2-V 6 O 8 2− further limits electron shuttling beyond the two m 2 -oxide-bound V centres, rendering its electronic structure more similar to the ligand-supported oxidebridged V dimers described above. 40,41 To further understand the origins of the observed V-O-V bond polarization, bond valence sum (BVS) calculations were performed. This technique correlates bond metrics about an atom to its oxidation state.…”

Design, Synthesis, and Applications of a Vanadium Complex: An Effective Catalyst for the Direct Conversion of Alcohols and Aldehydes to Esters

“…Based on our recent experience in designing a redox noninnocent phenalenyl-based copper­(II) complex for the selective oxidation of polycyclic aromatic hydrocarbons (PAHs), we became interested in designing a novel V-complex [(L 2 )­V IV O]­(ClO 4 ) as a catalyst toward additive-free oxidation of aldehydes and alcohols to esters in a one-pot manner. The new V-complex [(L 2 )­V IV O]­(ClO 4 ) was synthesized by a reaction of a methanolic solution of VOSO 4 (0.023 g, 0.140 mmol), methanol-suspended ligand HL 2 (0.05 g, 0.140 mmol), and Et 3 N­(0.014 g, 0.140 mmol), which resulted in the development of a brown solution within 10 min.…”