An oxidovanadium(IV) complex with 4,4′-di-tert-butyl-2,2′-bipyridine ligand: Synthesis, structure and catalyzed cyclooctene epoxidation

Iakov Fomenko (1) , Sandrine Vincendeau (2) , Eric Manoury (2) , Rinaldo Poli (2, 3) , Pavel Abramov (1) , Vladimir Nadolinny (1) , Maxim Sokolov (1, 4) , Artem Gushchin (1, 4)

1 NIC - Nikolaev Institute of Inorganic Chemistry [Novosibirsk]
2 LCC - Laboratoire de chimie de coordination
3 IUF - Institut universitaire de France
4 NSU - Novosibirsk State University

The interaction of vanadium(III) chloride (VCl3) with 4,4'-di-tert-butyl-2,2'-bipyridine (dbbpy) in air resulted in the monomeric oxidovanadium(IV) complex [VOCl2 (dbbpy)(H2O)] (1) in high yield. The complex was characterized by IR and EPR spectroscopies, by elemental analysis, and by single crystal X-ray diffraction analysis. The vanadium atom has a distorted octahedral coordination environment. The EPR spectrum of 1 in CH2Cl2 demonstrates an eight-line signal typical of vanadium(IV) with a d(1) electronic configuration. Complex 1 exhibits catalytic activity in the cyclooctene oxidation with tert-butyl hydroperoxide (TBHP) in CHCl3. Detailed EPR, NMR and GC-MS studies of the reaction revealed a few mechanistic details and the nature of by-products that are generated by involvement of the chloroform solvent.

Mots clés: Oxidovanadium(IV) complexes; 2 2'-bipyridine ligands; Crystal structure; EPR spectroscopy; Cyclooctene epoxidation

Domaines: Chimie de coordination; Catalyse; Chimie organique

Iakov Fomenko, Sandrine Vincendeau, Eric Manoury, Rinaldo Poli, Pavel Abramov, et al.. An oxidovanadium(IV) complex with 4,4′-di-tert-butyl-2,2′-bipyridine ligand: Synthesis, structure and catalyzed cyclooctene epoxidation. Polyhedron, 2020, 177, pp.114305. ⟨10.1016/j.poly.2019.114305⟩. ⟨hal-02563748⟩