Methane constitutes the largest fraction of natural gas reserves and is a low-cost abundant starting material for the synthesis of value-added chemicals and fuel. Selective catalytic functionalization of methane remains a vital goal in the chemical sciences due to its low intrinsic reactivity. Borylation has recently emerged as a promising route for the catalytic functionalization of methane. A major challenge in this regard is selective borylation towards the monoborylated product that is more active than methane and can easily lead to over-functionalization. Herein, we report a highly selective microporous metal−organic-framework-supported iridium(iii) catalyst for methane borylation that exhibits a chemoselectivity of >99% (mono versus bis at 19.5% yield; turnover number = 67) for monoborylated methane, with bis(pinacolborane) as the borylation reagent in dodecane, at 150 °C and 34 atm of methane. The preference for the monoborylated product is ascribed to the shape-selective effect of the metal−organic framework pore structures.

甲烷是天然气储量最大的部分，是合成增值化学品和燃料的低成本，丰富的起始原料。甲烷的选择性催化官能化由于其固有的低反应性而仍是化学科学中的重要目标。最近，硼化已成为甲烷催化功能化的有前途的途径。在这方面的主要挑战是向单硼化产物的选择性硼化，该单硼化产物比甲烷更具活性，并容易导致过度官能化。在此，我们报道了高度选择性的微孔金属-有机框架支撑的铱（iii）的甲烷硼化催化剂，在150°C和34 atm的温度下，对十二烷基化的单硼化甲烷甲烷具有化学选择性> 99％（单对双以19.5％的收率;营业额= 67）。甲烷。对单硼化产物的偏爱归因于金属-有机骨架孔结构的形状选择作用。