LNL-Carbazole Pincer Ligand: More than the Sum of Its Parts,Chemical Reviews

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LNL-Carbazole Pincer Ligand: More than the Sum of Its Parts
Chemical Reviews ( IF 51.4 ) Pub Date : 2023-06-23 , DOI: 10.1021/acs.chemrev.3c00202
George Kleinhans ₁ , Aino J Karhu ₁ , Hugo Boddaert ₁ , Sadia Tanweer ₁ , David Wunderlin ₁ , Daniela I Bezuidenhout ₁

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The utility of carbazole in photo-, electro-, and medicinal applications has ensured its widespread use also as the backbone in tridentate pincer ligands. In this review, the aim is to identify and illustrate the key features of the LNL-carbazolide binding to transition metal centers (with L = flanking donor moieties, e.g., C, N, P, and O-groups) in a systematic bottom-up progression to illustrate the marked benefits attainable from (i) the rigid aromatic carbazole scaffold (modulable in both the 1,8- and 3,6-positions), (ii) the significant electronic effect of central carbazole-amido binding to a metal, and the tunable sterics and electronics of both the (iii) flanking donor L-moieties and (iv) the wingtip R-groups on the L-donors, with their corresponding influence on metal coordination geometry, d-electron configuration, and resultant reactivity. Systematic implementation of the ligand design strategies not in isolation, but in a combinatorial approach, is showcased to demonstrate the potential for functional molecules that are not only modulable but also adaptable for wide-ranging applications (e.g., stereoselective (photo)catalysis, challenging small molecule activation, SET and redox applications, and even applications in chemotherapeutics) as an indication of future research efforts anticipated to stem from this versatile pincer assembly, not only for the transition metals but also for s-, p-, and f-block elements.

中文翻译：

LNL-咔唑钳形配体：不仅仅是各个部分的总和

咔唑在光、电和医学应用中的用途确保了其广泛用作三齿钳配体的主链。在本综述中，目的是确定并说明LNL -咔唑化物与过渡金属中心（L = 侧翼供体部分，例如 C、N、P 和 O 基团）结合的系统底部-的关键特征。向上的进展以说明（i）刚性芳族咔唑支架（在1,8-和3,6-位置均可调节），（ii）中心咔唑酰胺基与金属结合的显着电子效应可实现的显着好处，以及 (iii) 侧翼供体L部分和 (iv) 翼尖R基团的可调空间和电子学L-供体，及其对金属配位几何形状、d-电子构型和所得反应性的相应影响。配体设计策略的系统实施不是孤立的，而是以组合的方法，展示了功能分子的潜力，这些分子不仅可调节，而且适用于广泛的应用（例如，立体选择性（光）催化，具有挑战性的小分子分子活化、SET 和氧化还原应用，甚至化疗中的应用）作为未来研究工作的一个指示，预计源于这种多功能钳组件，不仅适用于过渡金属，而且适用于 s- 、 p-和f-嵌段元素。

更新日期：2023-06-23

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