Utilizing collective forces between reactant and multiple catalyst molecules has been unprecedented due to the difficulty in realizing high order catalysis. Inspired by the power of collective forces in enzymes and organic catalysts, herein we report a rare example of high order catalysis for ring opening reaction (ROR) of strained rings by methanol. ROR is an important way to produce various polysiloxanes, but usually suffers from serious side reactions especially at high conversion, and currently there is a need to design new reaction pathway to achieve low molecular dispersity. In our study, the judiciously designed strained spiral cyclosiloxanes enable a high order catalysis by methanol, and this new methodology leads to a cyclic polysiloxane with high molecular weight and low dispersity even at full conversion of reactants. Kinetic study indicates an extremely unusual high‐order reaction involving multiple methanol molecules per reaction, also confirmed by quantum calculation which reveals the presence of zwitterionic ions stabilized by collecting force of hydrogen bonds by methanol molecules. The inherent driving force for this unusual phenomenon is dominated by enthalpy stabilization of the reactive intermediates through hydrogen bonding. The selective formation of SiOSi bonds, instead of silanol products, reflects the power of scientific design.

中文翻译：

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制备大尺寸，窄分布的独特环状聚硅氧烷的反应

由于难以实现高阶催化，利用反应物与多个催化剂分子之间的集体力是前所未有的。受酶和有机催化剂中集体力量的启发，在此我们报告了一个罕见的例子，该例子是甲醇对应变环的开环反应（ROR）进行高阶催化。ROR是生产各种聚硅氧烷的重要方法，但是通常遭受严重的副反应，特别是在高转化率下，并且目前需要设计新的反应途径以实现低分子分散性。在我们的研究中，审慎设计的应变螺旋环硅氧烷使甲醇能够进行高阶催化，并且这种新方法导致即使在反应物完全转化的情况下，环状聚硅氧烷也具有高分子量和低分散性。动力学研究表明，每个反应涉及多个甲醇分子的极不寻常的高阶反应，也通过量子计算得到证实，量子计算揭示了两性离子离子的存在，该两性离子离子通过甲醇分子收集氢键的力得以稳定。这种异常现象的内在驱动力主要是通过氢键使反应性中间体的焓稳定。硅的选择性形成 Ø  Si键，而不是硅醇的产品，体现了科学设计的力量。