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

The polyoxometalate H5PV2Mo10O40 mediates the insertion of an oxygen atom from H5PV2Mo10O40 into the tin–carbon 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 H5PVV 2Mo10O40 to yield the i...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2013-12, Vol.135 (51), p.19304-19310
Main Authors: Khenkin, Alexander M, Efremenko, Irena, Martin, Jan M. L, Neumann, Ronny
Format: Article
Language:English
Online Access:Get full text
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Summary:The polyoxometalate H5PV2Mo10O40 mediates the insertion of an oxygen atom from H5PV2Mo10O40 into the tin–carbon 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 H5PVV 2Mo10O40 to yield the ion pair n-Bu4Sn•+–H5PVIVVVMo10O40. The H5PVIVVVMo10O40 moiety was identified by UV–vis and EPR. DFT calculations show that n-Bu4Sn•+–H5PVIVVVMo10O40 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.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja409559h