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Eccentricities in Spectroscopy and Reactivity of Non‐Heme Metal Intermediates Contained in Bispidine Scaffolds
Israel Journal of Chemistry ( IF 2.3 ) Pub Date : 2020-07-20 , DOI: 10.1002/ijch.202000045
Gourab Mukherjee 1 , Chivukula V. Sastri 1
Affiliation  

Ligand framework in a metal complex has a pivotal role to play in orchestrating the spectroscopic and reactivity parameters. High‐valent non‐heme metal intermediates are known to be crucial species in the catalytic cycles of several metalloenzymes. Among the plethora of a variety of ligand frameworks employed in bioinorganic chemistry, the bispidine molecular scaffold is unique and privileged. In this review, we intend to discuss the overwhelming effects of the bispidine ligand scaffold in tuning the spectroscopic signatures and reactivity parameters of non‐heme metal intermediates. The basic skeleton constituting a fused and rigid bicyclic diamine framework with its tentacles tethered to C2, C4, N3 and N7 provides tuneable features to both the primary and secondary coordination spheres. Therefore, the bispidine framework offers a handle to optimize the balance of rigidity and flexibility in a coordination molecule which is thereby important in understanding the rich but surprising results in the reactivity of metal intermediates contained in these scaffolds. Herein, we summarize the significant developments in different types of oxidation reactions of reactive metal intermediates stabilized in bispidine ligands and noted their mechanistic details.

中文翻译:

联苯吡啶支架中非血红素金属中间体的光谱异常和反应活性

金属络合物中的配体骨架在协调光谱和反应性参数方面起着关键作用。众所周知,高价非血红素金属中间体是几种金属酶催化循环中的关键物种。在生物无机化学中使用的多种配体构架中,双联吡啶分子支架是独特而独特的。在这篇综述中,我们打算讨论联吡啶的配体支架在调节非血红素金属中间体的光谱特征和反应性参数方面的压倒性作用。构成稠密且刚性的双环二胺骨架的基本骨架,其触角束缚在C2,C4,N3和N7上,可为一级和二级配位球提供可调节的功能。因此,Bispidine骨架为优化配位分子中的刚性和柔韧性之间的平衡提供了一种方法,因此对于理解这些支架中所含金属中间体的反应性丰富而出人意料的结果非常重要。在此,我们总结了在双联吡啶配体中稳定的反应性金属中间体在不同类型的氧化反应中的重要进展,并指出了其机理细节。
更新日期:2020-07-20
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