FLP Zintl Clusters for Small Molecule Activation and Catalysis

用于小分子活化和催化的 FLP Zintl 簇

• 批准号: EP/V012061/2
• 负责人: Meera Mehta
• 金额: $ 5.45万
• 依托单位: University of Oxford
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2024
• 资助国家: 英国
• 起止时间: 2024 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FV012061%2F2
• 关键词: FLP; Zintl; Clusters; Small; Molecule

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.

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采用，并直接应用于制药和聚合物行业。这一转变的重要性体现在诺贝尔奖在该领域获得的数量之多（格利尼亚、迪尔斯、阿尔德、维蒂格、齐格勒、纳塔、格鲁布斯、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（例如钯），由于存在多种稳定的氧化态，因此可以充当电子库。然而，与其使用相关的高运营成本引发了对基于主族元素的替代催化剂的研究。主族催化剂最成功的例子是受挫路易斯对（FLP），该系统同时具有贫电子和富电子位点。在该研究项目中，以Zintl簇（p-块的聚阴离子簇）作为富电子组分的FLP系统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，活化二氧化碳分子并将其连接在一起是这项工作的备受瞩目的目标。与其他 FLP 系统不同，簇组件可以理解为具有多种氧化态的电子库。此外，这些簇能够进行多位点激活，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 簇是这种化学特别有吸引力的候选者，因为它们是较大固态系统的分子类似物（因此可以作为多相催化剂的模型）。这项工作的发现非常重要，因为它们为用地球上丰富的替代品（即 Pd：44.29 美元/克；P：0.04 美元/克）取代基于贵金属的催化剂奠定了基础，从而形成了一个关键过程在全球范围内实施更具可持续性。此外，开发催化开采空气燃料的系统（通过回收温室气体二氧化碳来生产碳氢化合物）有助于全球实现清洁增长和应对人类面临的最大挑战——气候变化。