Alkyne gem-Hydrogenation: Formation of Pianostool Ruthenium Carbene Complexes and Analysis of Their Chemical Character
Alkyne gem-Hydrogenation: Formation of Pianostool Ruthenium Carbene Complexes and Analysis of Their Chemical Character
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DOI：
10.1002/anie.201904255
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发表时间：
2019-06-24
影响因子：
16.6
通讯作者：
Fuerstner, Alois
中科院分区：
文献类型：
--
作者：
Biberger, Tobias;Gordon, Christopher P.;Fuerstner, Alois
仲氢（p-H-2）诱导极化（PHIP）NMR光谱表明，[（CpRu）-Ru-X]配合物的电子性质有很大的不同，总是从事炔丙醇衍生物的偕氢化与形成pianostool钌卡宾;在这样做时，少电子丰富的Cp-X环降低的障碍，稳定所得的复合物，因此提供了利用真正的卡宾反应性的机会。通过DFT辅助分析固态（CNMR）-C-13光谱测定的化学位移张量，研究了所得钌配合物的化学性质。结合实验和计算数据绘制了一个家庭的钌卡宾，融合纯粹的亲电行为与特征更适合复分解活性格拉布斯型催化剂的肖像。
Parahydrogen (p-H-2) induced polarization (PHIP) NMR spectroscopy showed that [(CpRu)-Ru-X] complexes with greatly different electronic properties invariably engage propargyl alcohol derivatives into gem-hydrogenation with formation of pianostool ruthenium carbenes; in so doing, less electron rich Cp-X rings lower the barriers, stabilize the resulting complexes and hence provide opportunities for harnessing genuine carbene reactivity. The chemical character of the resulting ruthenium complexes was studied by DFT-assisted analysis of the chemical shift tensors determined by solid-state (CNMR)-C-13 spectroscopy. The combined experimental and computational data draw the portrait of a family of ruthenium carbenes that amalgamate purely electrophilic behavior with characteristics more befitting metathesis-active Grubbs-type catalysts.