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Key factors in pincer ligand design
Chemical Society Reviews ( IF 40.4 ) Pub Date : 2018-02-12 00:00:00 , DOI: 10.1039/c7cs00693d Eduardo Peris 1, 2, 3, 4 , Robert H. Crabtree 5, 6, 7, 8
Chemical Society Reviews ( IF 40.4 ) Pub Date : 2018-02-12 00:00:00 , DOI: 10.1039/c7cs00693d Eduardo Peris 1, 2, 3, 4 , Robert H. Crabtree 5, 6, 7, 8
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Pincers, tridentate ligands that prefer a meridional geometry, are a rising class because of their distinctive combination of properties. They permit a good level of control on the nature of the coordination sphere by holding the donor groups in a predictable arrangement. Some groups, such as an aryl or a pyridine, that would normally be easily lost as monodentate ligands, become reliably coordinated, especially if they form the central donor unit of the three. Many pincer complexes show exceptional thermal stability, a property that is particularly prized in homogeneous catalysis where they can permit high temperature operation. The connectors between the three donor groups are often rigid, enforcing a strict mer geometry but flexible linkers permit fac binding and even fluxionality between the two forms. Rigid pincers can make good ligands for asymmetric catalysis—if the wingtip groups cannot easily rotate they may instead maintain a geometry in which suitable substituents project into the active site area of the catalyst where they help enantio-differentiation of the relevant transition states. Examples have been selected to illustrate these and other properties of this promising ligand class.
中文翻译：
钳式配体设计的关键因素
钳子是倾向于子午几何的三齿配体，由于其独特的性能组合而成为新兴阶级。通过使捐助者团体保持可预见的安排，它们可以很好地控制协调领域的性质。通常容易以单齿配体丢失的某些基团（例如芳基或吡啶）变得可靠地配位，尤其是当它们形成这三个基团的中央供体单元时。许多钳状配合物表现出出色的热稳定性，这一特性在均相催化中尤为突出，因为在均相催化中它们可以进行高温操作。这三个供体基团之间的连接器通常是刚性的，从而实现了严格的mer几何形状，但灵活的连接器允许fac两种形式之间具有约束力甚至是流动性。刚性钳子可以成为不对称催化的良好配体-如果翼尖基团不能轻松旋转，它们可能会保持几何结构，其中合适的取代基伸入催化剂的活性位点区域，从而有助于相关过渡态的对映体分化。选择了一些实例来说明这种有前途的配体类别的这些和其他性质。
更新日期：2018-02-12
中文翻译：
钳式配体设计的关键因素
钳子是倾向于子午几何的三齿配体，由于其独特的性能组合而成为新兴阶级。通过使捐助者团体保持可预见的安排，它们可以很好地控制协调领域的性质。通常容易以单齿配体丢失的某些基团（例如芳基或吡啶）变得可靠地配位，尤其是当它们形成这三个基团的中央供体单元时。许多钳状配合物表现出出色的热稳定性，这一特性在均相催化中尤为突出，因为在均相催化中它们可以进行高温操作。这三个供体基团之间的连接器通常是刚性的，从而实现了严格的mer几何形状，但灵活的连接器允许fac两种形式之间具有约束力甚至是流动性。刚性钳子可以成为不对称催化的良好配体-如果翼尖基团不能轻松旋转，它们可能会保持几何结构，其中合适的取代基伸入催化剂的活性位点区域，从而有助于相关过渡态的对映体分化。选择了一些实例来说明这种有前途的配体类别的这些和其他性质。
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