Polyoxometalate-Catalyzed Insertion of Oxygen from O2 into Tin–Alkyl Bonds

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• 作者：Alexander M. Khenkin ; Irena Efremenko ; Jan M. L. Martin ; Ronny Neumann
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：December 26, 2013
• 年：2013
• 卷：135
• 期：51
• 页码：19304-19310
• 全文大小：481K
• ISSN：1520-5126

文摘

The polyoxometalate H₅PV₂Mo₁₀O₄₀ mediates the insertion of an oxygen atom from H₅PV₂Mo₁₀O₄₀ into the tin鈥揷arbon bond of n-Bu₄Sn through its activation by electron transfer to yield 1-butanol and (n-Bu₃Sn)₂O. The reaction is initiated by electron transfer from n-Bu₄Sn to H₅PV^V₂Mo₁₀O₄₀ to yield the ion pair n-Bu₄Sn^鈥?鈥揌₅PV^IVV^VMo₁₀O₄₀. The H₅PV^IVV^VMo₁₀O₄₀ moiety was identified by UV鈥搗is and EPR. DFT calculations show that n-Bu₄Sn^鈥?鈥揌₅PV^IVV^VMo₁₀O₄₀ is relatively unstable and forms more stable Bu⁺ and Bu₃Sn⁺ cations coordinated to the polyoxometalate, which were also identified by ESI-MS. Products are released at higher temperatures. In the presence of molecular oxygen as the terminal oxidant the reaction is catalytic.