Repozytorium
Wyszukaj
Kolekcje
Inne
Investigation of vanadium(III) and vanadium(IV) compounds supported by the linear diaminebis(phenolate) ligands : correlation between structures and magnetic properties.
Autorzy
Rok wydania
2021
Czasopismo
Numer woluminu
50
Strony
5184-5196
DOI
10.1039/d0dt04302h
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
A family of oxidovanadium(IV) compounds containing linear diaminebis(phenolate (salans) L1–5 ligands (L1 = [MeNCH2CH2NMe(CH2-4-CMe2CH2CMe3-C6H3O)2]2−; L2 = [MeNCH2CH2NMe(CH2-4-CH3-C6H3O)2]2−; L3 = [MeNCH2CH2NMe(CH2-4-Cl-C6H3O)2]2−; L4 = {MeNCH2CH2NMe[CH2-4,6-(CH3)2-C6H2O]2}2−; and L5 = {MeNCH2CH2NMe[CH2-4,6-(Br)2-C6H2O]2}2−) and non-oxidovanadium(III) with L2,4 and acac ligands has been prepared and characterized by chemical and physical techniques. Reactions of [VO(acac)2] with ligand precursors H2L2,4 in toluene or hexane afforded vanadium(III) compounds [V(L-κ4ONNO)(acac)] (1, L2; 2, L4), while the use of acetonitrile or ethanol led to the formation of dimeric oxidovanadium(IV) [(VO)2(μ-L-κ4ONNO)2] (3, L1; 4, L2; 5, L3) and monomeric [VO(L-κ4ONNO)] (6, L4, 7, L5) compounds. As shown by X-ray crystallography, compounds 1 and 2 are monomeric, in which the chelating ligands afford octahedral cis-α geometry at the vanadium center. In the dimeric structures of 3–5, the six-coordinate vanadium centers are bridged via two oxygen atoms of the L1–3 ligands while the L4,5 ligands generate square pyramidal structures of the monomeric 6 and 7 compounds. HFEPR studies allowed the determination of the spin Hamiltonian parameters of the S = 1 spin state of the monomeric V(III) and dimeric V(IV), and S = ½ in monomeric V(IV) compounds. Magnetic measurements of 3–5 indicated weak ferromagnetic metal–metal exchange interactions. A reaction course for the deoxygenation and reduction of vanadyl-salan compounds is proposed.
Adres publiczny
http://dx.doi.org/10.1039/d0dt04302h