This review focuses on the design, synthesis, and reactivity of low-coordinate base transition metal complexes supported by bulky alkoxide ligands. The unique electronic features of alkoxide ligands result in strongly electrophilic character at the metal centers, which enhances reactivity of metal-bound substrates and facilitates their transformation. However, insufficiently bulky alkoxide ligands tend to form oligomeric and polymeric aggregates, thus circumventing well-defined reactivity at isolated metal centers. This review examines first the requirements for the attainment of mononuclear complexes in alkoxide ligand environments. Coordination chemistry of the most prominent alkoxide ligands [OCR₃] is discussed, with particular emphasis on the impact of the R group on the nuclearity of the resulting complex and the number of alkoxide ligands bound to it. Next, the behavior of such complexes in group transfer chemistry and ensuing reactivity is examined. While several previously synthesized alkoxide ligands are discussed, the major focus of this review is on the recent chemistry of the “asymmetric” alkoxide ligands [OC^tBu₂Me] and [OC^tBu₂Ph] with the middle and late 3d metals.

这篇综述集中于由庞大的醇盐配体支持的低配位碱过渡金属配合物的设计，合成和反应性。醇盐配体的独特电子特征导致在金属中心具有强烈的亲电特性，从而增强了与金属结合的底物的反应性并促进了它们的转化。但是，体积不足的醇盐配体往往会形成低聚物和聚合物聚集体，从而在孤立的金属中心规避了明确定义的反应性。本文首先考察了在醇盐配体环境中达到单核络合物的要求。最突出的醇盐配体的配位化学[OCR ₃讨论]，特别强调R基团对所得配合物的核性的影响以及与其结合的醇盐配体的数目。接下来，研究了这种络合物在基团转移化学中的行为以及随之而来的反应性。虽然若干先前合成的醇盐配体进行了讨论，该评价的主要重点是在最近的“非对称”的醇盐配体[OC的化学^吨卜₂我]和[OC^吨卜₂ PH]与中间和后期的3d金属。