FLP Zintl Clusters for Small Molecule Activation and Catalysis

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采用，直接应用于制药和聚合物工业。这种转变的重要性反映在竞技场颁发的诺贝尔奖数量上（格里尼亚德;迪尔斯，桤木;维蒂希;齐格勒，纳塔;格拉布斯，施罗克，肖万;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，这些贵金属可以充当电子库。然而，与其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。主族催化剂的最成功的例子是受抑的刘易斯对（FLP），即具有贫电子和富电子位点的系统。在这项研究计划中，FLP系统与Zintl集群（聚阴离子集群的p-块）作为富电子成分将用于小分子活化和随后的碳-碳键形成化学。鉴于其对环境的恶劣影响，激活并将二氧化碳分子连接在一起是这项工作的重要目标。与其他FLP系统不同，团簇组分可以被理解为具有多个氧化态的电子库。此外，这些簇能够进行多位点活化，使多个二氧化碳分子处于正确的构型，以进行进一步的碳-碳键形成化学反应。Zintl簇是这种化学的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（因此可以作为非均相催化剂的模型）。这项工作的发现很重要，因为它们为用地球丰富的替代品取代基于贵金属的催化剂奠定了基础（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。此外，开发催化开采空气燃料的系统（通过回收绿色家庭气体二氧化碳来提供碳氢化合物）有助于全球实现清洁增长和应对人类最大的挑战-气候变化。

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 research programme, 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. Given its nefarious environmental impact, activation and linking carbon dioxide molecules together is the high-profile target for this work. Unlike other FLP systems, the cluster component can be understood as an electron reservoir with access to multiple oxidation states. Additionally, these clusters are capable of multi-site activation, bringing multiple carbon dioxide molecules in the right configuration to undergo further 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. Further, developing systems that catalytically mine the air for fuel (by recycling the green house gas carbon dioxide to afford hydrocarbons) contributes to global efforts towards Clean Growth and addressing humanity's greatest challenge - climate change.