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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
C-H activation by a diselenido dinickel(II) complex
Jessica Wallick1, Charles G Riordan, Glenn P A Yap
1Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
Journal of the American Chemical Society
|September 27, 2013
Summary
Selenium addition to a nickel(I) complex forms a dinickel(II) diselenido complex. This complex can oxidize substrates and convert between selenium forms, showcasing dynamic selenium chemistry in nickel complexes.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Coordination Chemistry
Background:
- Nickel complexes are versatile catalysts in various chemical transformations.
- Selenium ligands play crucial roles in biological systems and inorganic catalysis.
- Understanding the reactivity of selenium-containing metal complexes is key to developing new catalytic processes.
Purpose of the Study:
- To synthesize and characterize a novel dinickel(II) diselenido complex.
- To investigate the redox behavior and reactivity of the synthesized complex.
- To explore the potential of this complex in substrate oxidation and selenium transfer reactions.
Main Methods:
- Synthesis of the nickel(I) precursor complex [Ni(Me4[12]aneN4)(CO)]PF6.
- Redox reaction with elemental selenium to form the dinickel(II) diselenido complex.
- X-ray crystallography to determine the structure of the diselenido complex.
- Oxidation reactions with 9,10-dihydroanthracene and 1,4-cyclohexadiene.
- Characterization of the resulting hydroselenide complex and its conversion back to the diselenido adduct.
Main Results:
- The addition of selenium to [Ni(Me4[12]aneN4)(CO)]PF6 yielded the dinickel(II) diselenido complex {[(Ni(Me4[12]aneN4)]2(Se2)}(PF6)2 in 70% yield.
- The crystal structure revealed a μ-η(2):η(2)-Se2 ligand with a Se-Se bond length of 2.379(13) Å.
- The dinickel(II) diselenido complex oxidized 9,10-dihydroanthracene and 1,4-cyclohexadiene upon heating, forming the terminal hydroselenide complex [Ni(Me4[12]aneN4)(SeH)]PF6.
- The hydroselenide complex was regenerated to the diselenido complex by reaction with a phenoxy radical.
Conclusions:
- A novel dinickel(II) diselenido complex was successfully synthesized and structurally characterized.
- The complex exhibits dynamic redox behavior, facilitating substrate oxidation and selenium transfer.
- This study highlights the potential of nickel-selenium complexes in catalytic applications involving redox processes and selenium chemistry.
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