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

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BYSTRICKY Roman ANTAL Peter) TATIERSKY Jozef SCHWENDT Peter GYEPES Robert ŽÁK Zdirad

Druh Článek v odborném periodiku
Časopis / Zdroj Inorganic Chemistry
Fakulta / Pracoviště MU

Přírodovědecká fakulta

Citace
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Doi http://dx.doi.org/10.1021/ic500066p
Obor Anorganická chemie
Klíčová slova KEGGIN STRUCTURE; HYDROGEN-PEROXIDE; DECAVANADATE ION; SOLID-STATE; OXIDATION; COMPOUND; POLYOXOMETALATE; BIOCHEMISTRY; SPECIATION; REACTIVITY
Popis Two novel heterometallic complexes [Cd(NH3)(6)][{VO-(O-2)(2)(OH)}(2){mu-Cd(NH3)(4)}] (2) and [{VO(O-2)(2)(Im)}(2){mu-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(O-2)(2)(OH)}(2-) ions are interconnected by a {mu-Cd(NH3)(4)}(2+) group. Compound 3 is a trinuclear neutral complex comprising two {VO(O-2)(2)(Im)}(-) ions and a single bridging {mu-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-mu-O bond orders and increased mu-O-V bond orders in 3, in accordance with the expected Jahn-Teller distortion of the latter complex.