An Oxo-Bridged Binuclear Vanadium(III) 2,2′-Bipyridine Complex and Its Vanadium(IV) and Vanadium(V) Oxidation Products

Brand S.G., Hawkins C.J., Edelstein N., Shalimoff G., Snow M.R. and Tiekink E.R.T. (1990) An Oxo-Bridged Binuclear Vanadium(III) 2,2′-Bipyridine Complex and Its Vanadium(IV) and Vanadium(V) Oxidation Products. Inorganic Chemistry, 29 3: 434-438. doi:10.1021/ic00328a018


Author Brand S.G.
Hawkins C.J.
Edelstein N.
Shalimoff G.
Snow M.R.
Tiekink E.R.T.
Title An Oxo-Bridged Binuclear Vanadium(III) 2,2′-Bipyridine Complex and Its Vanadium(IV) and Vanadium(V) Oxidation Products
Journal name Inorganic Chemistry
ISSN 1520510X 00201669
Publication date 1990-02-01
Sub-type Article (original research)
DOI 10.1021/ic00328a018
Volume 29
Issue 3
Start page 434
End page 438
Total pages 5
Language eng
Subject 1606 Physical and Theoretical Chemistry
1604 Inorganic Chemistry
Abstract Vanadium(III) in water reacts with 2,2′-bipyridine to form an oxo-bridged binuclear complex that crystallizes as [{VCl-(bpy)]O],Cl·3HO in the orthorhombic space group Pbcn with unit cell dimensions a = 18.820 (8) Å, b = 9.507 (2) Å, c = 25.792 (6) Å, V = 4614.8 Å, and Z = 8. The complex in its crystalline form has a magnetic moment per vanadium of 3.176 ± 0.002 µ, an unusually high value, considering all available evidence supports the III oxidation state. Aerial oxidation yields an oxovanadium(IV) complex that crystallizes from an aqueous acetone perchlorate solution as [VOCl(bpy)]ClOin the monoclinic space group P2/c with a = 12.960 (3) Å, b = 12.310 (4) Å, c = 13.642 (3) Å, β = 105.78 (2)°, V = 2094.4 Å, and Z = 4. Further oxidation in aqueous tetrahydrofuran produces crystals of [VO(bpy)]Cl·4HO with the triclinic space group Pl with a = 1 1.527 (5) Å, b = 15.102 (5) Å, c = 6.738 (3) Å, ± = 97.33 (4)Å, ² = 97.26 (4)°, γ = 101.31 (3)°, V= 1126.9 Å, and Z = 2. The structures of the first and third complexes were refined by a full-matrix least-squares procedure, and a blocked-matrix procedure was employed for the refinement of the vanadyl complex. Refinement on 2364 statistically significant reflections yielded final R = 0.063 and R= 0.071 for the oxo-bridged complex; on 2402 reflections, R = 0.065 and R= 0.071 for the vanadyl complex; and on 2212 reflections, R = 0.076 and R= 0.084 for the dioxovanadium(V) complex. The coordination geometries show similar distortions from a regular octahedral structure dictated by repulsions between the two anionic ligands, the small bite angle of the chelates, and the effects of trans ligands on the coordinate bond lengths. The binuclear complex has a Caxis relating the two units, which are twisted 61.6° relative to each other. The V-O-V group is close to linear with a bond angle of 173.5 (4)°.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Scopus Import
 
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