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)
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https://figshare.com/articles/dataset/Peroxido_Complexes_of_Vanadium_V_as_Ligands_Crystal_Structures_of_Cd_NH_sub_3_sub_sub_6_sub_VO_O_sub_2_sub_sub_2_sub_OH_sub_2_sub_Cd_NH_sub_3_sub_sub_4_sub_and_VO_O_sub_2_sub_sub_2_sub_Im_sub_2_sub_Cu_Im_sub_4_sub_Im_Imidazole_/2562679
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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.
创建时间：
2016-02-22
