Bypassing a highly unstable frustrated Lewis pair: dihydrogen cleavage by a thermally robust silylium-phosphine adduct
Bypassing a highly unstable frustrated Lewis pair: dihydrogen cleavage by a thermally robust silylium-phosphine adduct
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DOI：
10.1039/c4cc05905k
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发表时间：
2014-01-01
影响因子：
4.9
通讯作者：
Ashley, Andrew E.
中科院分区：
文献类型：
--
作者：
Herrington, Thomas J.;Ward, Bryan J.;Ashley, Andrew E.
热稳定的甲硅烷基鎓络合物[iPr（3）Si-PtBu 3]（+）[B（C6 F5）（4）]（-）（1）在90 ℃下活化H-2/D-2（PhCl）; DFT计算表明，H-2的断裂是通过Si-P键的伸长直接从加合物中形成碰撞络合物进行的，从而避免了iPr（3）Si（+）-PtBu 3 FLP的不可分离性。
The thermally robust silylium complex [iPr(3)Si-PtBu3](+)[B(C6F5)(4)](-) (1) activates H-2/D-2 at 90 degrees C (PhCl); no evidence for dissociation into the separated Lewis pair is found. DFT calculations show H-2 cleavage proceeds via Si-P bond elongation to forman encounter complex directly from the adduct, thus avoiding the non-isolable iPr(3)Si(+)-PtBu3 FLP.