This perspective summarizes our group's extensive research in the realm of organometallic lanthanide complexes, while also placing the catalytic reactions supported by these species within the context of known lanthanide catalysis worldwide, with a specific focus on phosphorus-based catalytic reactions such as intermolecular hydrophosphination and hydrophosphinylation. α-Metalated N,N-dimethylbenzylamine ligands have been utilized to generate homoleptic lanthanide complexes, which have subsequently proven to be highly active lanthanum-based catalysts. The main goal of our research program has been to enhance the catalytic efficiency of lanthanum-based complexes, which began with initial successes in the stoichiometric synthesis of organometallic lanthanide complexes and utilization of these species in catalytic hydrophosphination reactions. Not only have these species supported traditional lanthanide catalysis, such as the hydrophosphination of heterocumulenes like carbodiimides, isocyanates, and isothiocyanates, but they have also been effective for a plethora of catalytic reactions tested thus far, including the hydrophosphinylation and hydrophosphorylation of nitriles, hydrophosphination and hydrophosphinylation of alkynes and alkenes, and the heterodehydrocoupling of silanes and amines. Each of these catalytic transformations is meritorious in its own right, offering new synthetic routes to generate organic scaffolds with enhanced functionality while concurrently minimizing both waste generation and energy consumption. Objectives: We aim for the research summary presented herein to inspire and encourage other researchers to investigate f-element based stoichiometric and catalytic reactions. Our efforts in this field began with the recognition that potassium salts of benzyldimethylamine preferred deprotonation at the α-position, rather than the ortho-position, and we wondered if this regiochemistry would be retained in the formation of lanthanide complexes. The pursuit of this simple idea led first to a series of structurally fascinating homoleptic organometallic lanthanide complexes with surprisingly good stability. Fundamental studies of the protonolysis chemistry of these complexes ultimately revealed highly versatile lanthanide-based precatalysts that have propelled a catalytic investigation spanning more than a decade. We anticipate that this summative perspective will animate the synthetic as well as biological communities to consider La(DMBA)₃-based catalytic methods in the synthesis of functionalized organic scaffolds as an atom-economic, convenient, and efficient methodology. Ultimately, we envision our work making a positive impact on the advancement of novel chemical transformations and contributing to progress in various fields of science and technology.

中文翻译：

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α-金属化N,N-二甲基苄胺稀土金属配合物及其催化应用

这一观点总结了我们小组在有机金属稀土配合物领域的广泛研究，同时还将这些物质支持的催化反应置于全球已知的稀土催化的背景下，特别关注磷基催化反应，例如分子间氢膦酸化和氢膦酰化。 α-金属化的N , N-二甲基苄胺配体已被用来生成均配镧系元素配合物，随后被证明是高活性的镧基催化剂。我们研究计划的主要目标是提高镧基络合物的催化效率，该计划首先在有机金属镧系元素络合物的化学计量合成以及这些物质在催化氢膦化反应中的利用方面取得了初步成功。这些物质不仅支持传统的镧系元素催化，例如碳二亚胺、异氰酸酯和异硫氰酸酯等杂累积烯的氢膦化，而且它们对于迄今为止测试的大量催化反应也有效，包括腈的氢膦酰化和氢磷酸化、氢膦化和氢膦酰化。炔烃和烯烃的氢膦酰化，以及硅烷和胺的杂脱氢偶联。这些催化转化中的每一种本身都有其优点，提供了新的合成路线来生成具有增强功能的有机支架，同时最大限度地减少废物产生和能源消耗。目标：我们的目的是通过本文提出的研究总结来启发和鼓励其他研究人员研究基于 f 元素的化学计量和催化反应。我们在这一领域的努力始于认识到苄基二甲胺的钾盐更喜欢在α位而不是邻位去质子化，我们想知道这种区域化学是否会在镧系元素络合物的形成中保留。对这个简单想法的追求首先导致了一系列结构上令人着迷的均配有机金属镧系元素络合物，并且具有令人惊讶的良好稳定性。对这些配合物的质子分解化学的基础研究最终揭示了高度通用的镧系元素预催化剂，推动了十多年来的催化研究。我们预计，这种总结性的观点将激励合成界和生物界考虑在功能化有机支架的合成中基于 La(DMBA) _{3 的}催化方法作为一种原子经济、方便且高效的方法。最终，我们希望我们的工作能够对新型化学转化的进步产生积极影响，并为各个科学技术领域的进步做出贡献。