title: 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.
authors.affiliation: Institute of Inorganic Chemistry, Slovak Academy of Sciences , Dúbravská cesta 9, 845 36 Bratislava 45, Slovak Republic.
authors.forename: Roman
authors.initials: R
authors.lastname: Bystrický
authors.forename: Peter
authors.initials: P
authors.lastname: Antal
authors.forename: Jozef
authors.initials: J
authors.lastname: Tatiersky
authors.forename: Peter
authors.initials: P
authors.lastname: Schwendt
authors.forename: Róbert
authors.initials: R
authors.lastname: Gyepes
authors.forename: Zdirad
authors.initials: Z
authors.lastname: Žák