Peroxido Complexes of Vanadium(V) as Ligands. Crystal Structures of [Cd(NH₃)₆][{VO(O₂)₂(OH)}₂{μ-Cd(NH₃)₄}] and [{VO(O₂)₂(Im)}₂{μ-Cu(Im)₄}] (Im = Imidazole)

Abstract

Two novel heterometallic complexes [Cd(NH3)6][{VO(O2)2(OH)}2{μ-Cd(NH3)4}] (2) and [{VO(O2)2(Im)}2{μ-Cu(Im)4}] (3) (Im = imidazole) containing peroxidovanadium complexes as metalloligands were prepared and characterized by spectral methods. X-ray single-crystal analysis revealed the presence of unique trinuclear complexes in the crystal structures of 2 and 3. The structure of 2 contains an anionic complex, whose two {VO(O2)2(OH)}(2-) ions are interconnected by a {μ-Cd(NH3)4}(2+) group. Compound 3 is a trinuclear neutral complex comprising two {VO(O2)2(Im)}(-) ions and a single bridging {μ-Cu(Im)4}(2+) group. The bonding via an equatorial OH(-) ligand in 2 and via a doubly bonded apical oxygen atom in 3 represents coordination modes previously unobserved for diperoxidovanadium complexes. Compared with complex 2, density functional theory studies reported decreased Cu-μ-O bond orders and increased μ-O-V bond orders in 3, in accordance with the expected Jahn-Teller distortion of the latter complex.

Heterometallic Copper–Vanadium Compounds: Crystal Structures of Polymers [Cu(im)4(V2O4(mand)2)]n and [Cu(im)4(V2O4((S)-mand)2)]n·2nH2O (im = imidazole, mand = mandelato2−)

“…[Cu(im) 4 (V 2 O 4 (mand) 2 ] n (1) and [Cu(im) 4 (V 2 O 4 ((S)mand) 2 )] n ·2nH 2 O (2) (mand = mandelato(2-) ligand) were prepared as a part of our continual research on heterometallic transition metal-vanadium compounds with potential applications in asymmetric catalysis or development of new anode materials for batteries [4,[6][7][8][9]. Herein, we discuss the unexpected polymeric structures of 1 and 2 that differ significantly from the heretofore characterized, mostly chiral, compounds.…”

“…Only three compounds contain unsubstituted imidazole ( im = imidazole), namely enantiomers {[Λ–Cu( en )( im ) 2 ][VO 3 ] 2 } n and {[Δ–Cu( en )( im ) 2 ][VO 3 ] 2 } n [ 2 ] and [Cu( im ) 4 ] 2 (V 4 O 12 ) [ 3 ]. There are only two compounds where an organic ligand is bound both to vanadium and copper atom: [{VO(O 2 ) 2 ( im )} 2 { µ –Cu( im ) 4 }] [ 4 ] and {Cu( im ) 4 [(VO 2 F 2 ( py )] 2 } ( py = pyridine) [ 5 ]. Both compounds described in this paper belong to this last group of rare compounds.…”

Trapping ionic dimers of dinuclear peroxido mandelato complexes of vanadium(V) into cavities constructed from Δ- and Λ-[Ni(phenanthroline)3]2+ cations: a precursor to Ni(VO3)2

“…In recent years, we have reported on transition metal-vanadium compounds, comprised of the combinations Mn-V [20], Fe-V, Ni-V [21,22] and Cu-V [23][24][25][26][27][28][29] that were investigated mostly for their chiral properties. In continuation of our studies on stereochemistry of vanadium(V) complexes, we present here the synthesis and…”