Department of Organic Chemistry, Weizmann Institute of Science , Rehovot, Israel 76100.
J Am Chem Soc. 2013 Dec 26;135(51):19304-10. doi: 10.1021/ja409559h. Epub 2013 Dec 13.
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 H5PV(V)2Mo10O40 to yield the ion pair n-Bu4Sn(•+)-H5PV(IV)V(V)Mo10O40. The H5PV(IV)V(V)Mo10O40 moiety was identified by UV-vis and EPR. DFT calculations show that n-Bu4Sn(•+)-H5PV(IV)V(V)Mo10O40 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.
多金属氧酸盐 H5PV2Mo10O40 通过电子转移使其活化，将 H5PV2Mo10O40 中的一个氧原子插入到 n-Bu4Sn 的锡-碳键中，生成 1-丁醇和 (n-Bu3Sn)2O。反应是由 n-Bu4Sn 向 H5PV(V)2Mo10O40 转移电子引发的，生成离子对 n-Bu4Sn(•+)-H5PV(IV)V(V)Mo10O40。通过 UV-vis 和 EPR 鉴定了 H5PV(IV)V(V)Mo10O40 部分。DFT 计算表明，n-Bu4Sn(•+)-H5PV(IV)V(V)Mo10O40 相对不稳定，形成更稳定的与多金属氧酸盐配位的 Bu(+)和 Bu3Sn(+)阳离子，这也通过 ESI-MS 进行了鉴定。产物在较高温度下释放。在分子氧作为末端氧化剂的存在下，反应是催化的。
