FLP Zintl Clusters for Small Molecule Activation and Catalysis

催化碳-碳键形成反应在合成化学中普遍存在，被学术研究人员和制造业广泛使用，直接应用于制药和聚合物工业。这一转变的重要性体现在竞技场上诺贝尔奖的绝对数量上(格利纳德；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，根吉，铃木)。目前影响这种转变的技术使用昂贵的贵金属(如钯)，由于可以获得多种稳定的氧化态，这些贵金属可以充当电子储存库。然而，与它们的使用相关的高昂的操作成本已经点燃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路易斯对(FLP)，这是一种既有贫电子中心又有富电子中心的体系。在这个研究计划中，以Zintl簇(p-嵌段的多阴离子簇)为富电子组分的FLP系统将被用于小分子活化和随后的碳-碳键形成化学。考虑到其对环境的有害影响，激活并将二氧化碳分子连接在一起是这项工作的高调目标。与其他FLP系统不同的是，团簇成分可以理解为一个电子储存库，可以访问多个氧化态。此外，这些簇能够进行多位激活，使多个二氧化碳分子以正确的构型进行进一步的碳-碳键形成化学。锌原子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)，使全球实施的关键进程更可持续。此外，开发催化开采空气以获取燃料的系统(通过回收温室气体二氧化碳来制造碳氢化合物)有助于全球努力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.