The abundance and structural diversity of hydroxide-containing secondary building units (SBUs) in metal–organic frameworks (MOFs) have provided unique opportunities for the development of transition metal (TM) catalysts. This minireview surveys the structures of hydroxide-containing SBUs and summarizes recently developed strategies for the generation of catalytically active metal complexes on these SBUs and direct transformation of SBU hydroxides to catalytically active species. The applications of SBU-based catalysts in various organic transformations are also discussed, along with comparisons with homogeneous benchmarks. Systematic studies of the conversion of SBUs to catalytically active species will reveal structure–reactivity relationships in this class of MOF catalysts and provide structural and functional models for traditional heterogeneous catalysts. Structure-based optimization of SBU-based catalysts promises to lead to highly efficient and low-cost novel TM catalysts with important roles in green chemistry and sustainability.

金属有机骨架（MOF）中含氢氧化物的二级建筑单元（SBU）的丰富性和结构多样性为过渡金属（TM）催化剂的开发提供了独特的机会。这份小型综述对含氢氧化物的SBU的结构进行了调查，并总结了最近开发的在这些SBU上生成催化活性金属配合物并将SBU氢氧化物直接转化为催化活性物质的策略。还讨论了SBU基催化剂在各种有机转化中的应用，以及与均相基准的比较。对SBU转化为催化活性物质的系统研究将揭示这类MOF催化剂的结构反应性关系，并为传统的非均相催化剂提供结构和功能模型。基于SBU的催化剂的基于结构的优化有望导致高效，低成本的新型TM催化剂，在绿色化学和可持续性方面发挥重要作用。