Grochowska-Tatarczak M, Koteras K, Kazimierczuk K, Malinowski P J
Centre of New Technologies, University of Warsaw, Banacha 2c, 02-093, Warsaw, Poland.
Chemistry. 2024 Aug 12;30(45):e202401322. doi: 10.1002/chem.202401322. Epub 2024 Jun 27.
The report introduces simple yet highly reactive calcium salt, Ca[Al(OR)] (R=C(CF)), 1, which effectively catalyses olefin hydrosilylation through an unusual mechanism involving the activation of the alkene molecule. Upon dissolution in o-difluorobenzene (oDFB), 1 forms a highly Lewis acidic [Ca(oDFB)] complex. Our DFT calculations reveal that fluoride ion affinity is comparable to SbF. Reactivity tests show that it effectively catalyses the hydrosilylation of olefins with high regioselectivity, also in reactions involving sterically demanding substrates like (iPr)SiH or tetrasubstituted olefins. Experimental and computational results point to the mechanism where the olefin molecule forms a complex with Ca, which significantly facilitates the attack of H-SiR on the C=C double bond.
该报告介绍了一种简单但反应活性高的钙盐Ca[Al(OR)]（R = C(CF)），即1，它通过一种涉及烯烃分子活化的不同寻常的机制有效地催化烯烃硅氢化反应。1溶解于邻二氟苯（oDFB）中时，会形成一种高路易斯酸性的[Ca(oDFB)]络合物。我们的密度泛函理论（DFT）计算表明，氟离子亲和力与SbF相当。反应活性测试表明，它能有效地催化烯烃的硅氢化反应，具有高区域选择性，在涉及空间位阻较大的底物如（iPr）SiH或四取代烯烃的反应中也是如此。实验和计算结果指向这样一种机制：烯烃分子与Ca形成络合物，这显著促进了H-SiR对C=C双键的进攻。
