Deposition of small metal-oxide clusters on the Zr-based nodes of a metal-organic framework has been demonstrated to provide access to a variety of single-site catalysts. Well-defined catalytic active sites are amenable to detailed computational studies of potential catalytic pathways, and they invite screening a wide range of metals to assess their expected activity. Here we report the application of density functional theory to a variety of transition metals (in particular Ti^IV, V^II, V^IV, Cr^II, Cr^III, Mn^II, Mn^IV, Fe^II, Fe^III, Ni^II, Co^II, Co^III, Cu^II, Cu^III, Pd^II, Mo^II, and W^II) supported on NU-1000 inorganometallic nodes to evaluate their activity for ethylene dimerization. We found that the rate-determining step varies between different catalysts, which illustrates the importance of considering more than a single step when comparing catalytic cycles across a variety of metals. Our calculations are consistent with the known good activity of supported Ni^II for ethylene dimerization, and they predict that Cr^II and Pd^II are also potentially useful catalysts for this process. We also screen modifications to the organic linker of Ni^II-NU-1000 by considering the addition of Me, iPr, tBu, CF₃ and NH₂ groups to study the influence of sterically demanding and, the case of CF₃ and NH₂, respectively, electron-donating and -withdrawing, substituents on the activity for ethylene dimerization; we predict no improvements in activity or selectivity (for 1-butene) with such substitutions.

已证明在金属有机框架的Zr基节点上沉积小金属氧化物簇可提供访问各种单中心催化剂的途径。定义明确的催化活性位点适合进行潜在催化途径的详细计算研究，并邀请您筛选各种金属以评估其预期活性。在这里，我们报告了密度泛函理论在各种过渡金属（尤其是Ti ^IV，V ^II，V ^IV，Cr ^II，Cr ^III，Mn ^II，Mn ^IV，Fe ^II，Fe ^III，Ni ^II，Co ^{II中的应用）的应用。}，公司^III，Cu ^II，Cu ^III，Pd ^II，Mo ^II和W ^II）负载在NU-1000无机金属节点上，以评估其对乙烯二聚作用的活性。我们发现，决定速率的步骤在不同的催化剂之间有所不同，这说明了比较多种金属的催化循环时，考虑多个步骤的重要性。我们的计算与已知的负载型Ni ^II对乙烯二聚的良好活性是一致的，并且他们预测Cr ^II和Pd ^II也是该过程的潜在有用催化剂。我们还筛选了对Ni ^II有机连接基的修饰-NU-1000，考虑添加Me，i Pr，t Bu，CF ₃和NH ₂基团，以研究空间需求的影响，以及CF ₃和NH _2的情况，分别研究给电子和吸电子，乙烯二聚活性上的取代基；我们预测此类取代不会提高活性或选择性（对1-丁烯）。