Synthesis and reactivity of oxo-peroxo-vanadium(V) bipyridine compounds.

Inorganic Chemistry
Christopher R WaidmannJames M Mayer

Abstract

The vanadium(IV) compound [V(IV)O(OH)((t)Bu(2)bpy)(2)]BF(4) (V(IV)O(OH)) ((t)Bu(2)bpy = 4,4'-di-tert-butylbipyridine) is slowly oxidized by O(2) in ethereal solvents to give the oxo-peroxo compound [V(V)O(O(2))((t)Bu(2)bpy)(2)]BF(4) (V(V)O(O(2))) in excellent yield. This and related compounds were fully characterized by NMR, IR, and optical spectroscopies; mass spectrometry; elemental analyses; and an X-ray crystal structure of the 4,4'-dimethylbipyridine analog, [V(V)O(O(2))(Me(2)bpy)(2)]BF(4). Monitoring the reaction of V(IV)O(OH) with O(2) in THF/acetonitrile mixtures by (1)H NMR and optical spectroscopies surprisingly shows that the initial product is the cis-dioxo compound [V(V)(O)(2)((t)Bu(2)bpy)(2)]BF(4) (V(V)O(2)), which then converts to V(V)O(O(2)). Reaction of V(IV)O(OH) with (18)O(2) gives ca. 60% triply (18)O labeled V(V)O(O(2)). The mechanism of formation of V(V)O(O(2)) is complex and may occur via initial reduction of O(2) at vanadium(IV) to give a superoxo-vanadium(V) intermediate, autoxidation of the THF solvent, or both. That V(V)O(2) is generated first appears to be due to the ability of V(IV)O(OH) to act as a hydrogen atom donor. For instance, V(IV)O(OH) reacts with V(V)O(O(2)) to give V(V)O(2). V(V)O(O(2)) i...Continue Reading

References

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Mar 19, 2009·Journal of the American Chemical Society·Christopher R WaidmannJames M Mayer
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Citations

Mar 6, 2013·Inorganic Chemistry·Sujoy RanaDebabrata Maiti
Mar 31, 2015·Inorganic Chemistry·Dominik Munz, Thomas Strassner
Aug 7, 2014·Inorganic Chemistry·Amanda E KingChristopher J Chang
Oct 23, 2012·Journal of the American Chemical Society·Anthony F CozzolinoCarl D Hoff
Jan 8, 2015·Organic & Biomolecular Chemistry·Wen-Chieh YangChien-Tien Chen
Dec 16, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Valeria Conte, Barbara Floris
Aug 30, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Harikleia SartziSpyros P Perlepes
Apr 23, 2021·Chemical Communications : Chem Comm·Rui ZhangJeffrey J Warren
Jul 16, 2019·Inorganic Chemistry·Yoshihiro Shimoyama, Takahiko Kojima

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