FB Chemie, TU Kaiserslautern, Erwin Schrödinger Strasse 52, 67663, Kaiserslautern, Germany.
Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avgda. Països Catalans, 16, 43007, Tarragona, Spain.
Chemistry. 2018 Oct 12;24(57):15178-15184. doi: 10.1002/chem.201802886. Epub 2018 Sep 11.
The mechanism of a trinuclear cooperative dehydrogenative C-N bond-forming reaction is investigated in this work, which avoids the use of chelate-assisting directing groups. Two new highly efficient Ru/Cu co-catalyzed systems were identified, allowing orders of magnitude greater TOFs than the previous state of the art. In-depth kinetic studies were performed in combination with advanced DFT calculations, which reveal a decisive rate-determining trinuclear Ru-Cu cooperative reductive elimination step (CRE).
本工作研究了一种避免使用螯合辅助导向基团的三联核协同脱氢 C-N 键形成反应的机理。确定了两种新的高效 Ru/Cu 共催化体系，其 TOF 比先前的最先进水平高出几个数量级。结合先进的 DFT 计算进行了深入的动力学研究，揭示了决定速率的三联核 Ru-Cu 协同还原消除步骤 (CRE)。
