Small Molecule Activation Using Zintl Clusters

催化碳-碳键形成反应在合成化学中无处不在，被学术研究人员和制造业广泛应用，在制药和聚合物工业中有直接应用。这一转变的重要性反映在这个领域获得的诺贝尔奖的数量上（格利格纳、迪尔斯、阿尔德、维蒂希、齐格勒、纳塔、格拉布斯、施罗克、肖文、赫克、根岸、铃木）。目前影响这种转变的技术采用昂贵的贵金属（如钯），由于多种稳定氧化态的可用性，它们可以作为电子储集层。然而，与它们的使用相关的高运营成本引发了基于主族元素的替代催化剂的研究。主基团催化剂最成功的例子是受挫的路易斯对（FLPs），即具有贫电子和富电子位点的系统。在这项工作中，以Zintl簇（p -嵌段的聚阴离子簇）为富电子组分的FLP体系将用于小分子活化和随后的碳-碳键形成化学。Zintl簇是这种化学特别有吸引力的候选者，因为它们是更大的固态系统的分子类似物（因此可以作为多相催化剂的模型）。这项工作的发现很重要，因为它们为用地球上丰富的替代品取代基于贵金属的催化剂(即Pd: 44.29美元/克；P: 0.04美元/克)，使全球实施的关键过程更具可持续性。

Catalytic carbon-carbon bond formation reactions are ubiquitous in synthetic chemistry, widely employed by academic researchers and within the manufacturing sector, with direct applications in the pharmaceutical and polymer industries. The importance of this transformation is reflected by the sheer number of Nobel prizes awarded in the arena (Grignard; Diels, Alder; Wittig; Ziegler, Natta; Grubbs, Schrock, Chauvin; Heck, Negishi, Suzuki). Current technologies to affect this transformation employ expensive precious metals (such as palladium) that can act as electron reservoirs due to the availability of multiple stable oxidation states. However, the high operational costs associated with their use has ignited the study of alternative catalysts based on main-group elements. The most successful examples of main-group catalysts are frustrated Lewis pairs (FLPs), systems that feature both an electron poor and electron rich site. In this work, FLP systems with Zintl cluster (polyanionic cluster of the p-block) as the electron-rich component will be employed in small molecule activation and subsequent carbon-carbon bond formation chemistry. Zintl clusters are particularly attractive candidates for this chemistry as they are molecular analogues of larger solid-state systems (and can thus act as models for heterogenous catalysts). Findings from this work are important as they build the groundwork to replace catalysts based on precious metals with earth-abundant alternatives (i.e. Pd: $44.29(USD)/g; P: $0.04(USD)/g), making a key process that is globally implemented more sustainable.