Deprotonated carboxamidate ‘N’ donors have been extensively explored as ligands to support metal ions with unusual higher oxidation states. Their ability to serve as both σ and π-electron donor, being resistant to oxidation and provide exceptional hydrolytic stability to a coordinated metal ion has altogether enhanced the broad applicability of carboxamidate ligands in bio-mimetic catalysis. Although the biological precedents with such class of ligands are very less (Nitrile hydratases, Bleomycin, nickel superoxide dismutases, etc.), the synthetic modelling of various metalloenzymes employing carboxamidate ligands have emerged rapidly in the past few decades. The present review accounts for the brief discussion on the unique electronic structure and coordination chemistry these ligands exhibit and exclusively outlines the significant developments in bio-mimetic oxidation chemistry with special reference to high valent metal oxidants and their reactivity towards organic substrates. The notable achievements obtained by using these classes of ligands stretches back to 1848 for the development of the popular biuret reaction followed by the exploration of bio-mimetic metal-peptide complexes, pyridylcarboxamides for stabilization high valent metal-oxo species of late first row transition metal ions. The design of urea based tripodalcarboxamide ligands by Borovik et al. to install hydrogen bonding interactions to stabilize oxo/hydroxo-metal complexes also renders significant development in the bio-inspired catalysis. To the best of our knowledge, the most important outcome of research employing carboxamide ligands has been the discovery of tetraamido macrocyclic ligands (TAMLs) by Collins and co-workers who managed to make seven generations of the Fe-TAML catalyst that find interesting applications.

已广泛探索去质子化的氨基甲酸酯“ N”供体作为配体，以支持具有异常高氧化态的金属离子。它们既可以充当σ电子供体，又可以充当π电子供体，具有抗氧化性，并能为配位金属离子提供出色的水解稳定性，从而完全提高了氨基甲酸酯配体在仿生催化中的广泛应用性。尽管具有这类配体的生物学先例很少（腈水合酶，博来霉素，镍超氧化物歧化酶等），但在过去的几十年中，采用羧酰胺基配体的各种金属酶的合成模型迅速出现。本文概述了这些配体所表现出的独特电子结构和配位化学的简短讨论，并专门概述了仿生氧化化学的重大进展，特别提到了高价金属氧化剂及其对有机底物的反应性。使用这些类型的配体获得的显著成就可追溯到1848年，以发展流行的缩二脲反应，随后探索了仿生物金属-肽络合物，吡啶基羧酰胺用于稳定第一排过渡金属的高价金属-氧代物种。离子。Borovik设计基于尿素的三脚架甲酰胺配体 使用这些类型的配体获得的显著成就可追溯到1848年，以发展流行的缩二脲反应，随后探索了仿生物金属-肽络合物，吡啶基羧酰胺用于稳定第一排过渡金属的高价金属-氧代物种。离子。Borovik设计基于尿素的三脚架甲酰胺配体 使用这些类型的配体获得的显著成就可追溯到1848年，以发展流行的缩二脲反应，随后探索了仿生物金属-肽络合物，吡啶基羧酰胺用于稳定第一排过渡金属的高价金属-氧代物种。离子。Borovik设计基于尿素的三脚架甲酰胺配体等。安装氢键键合相互作用以稳定氧代/氢氧代金属络合物也使生物启发性催化技术取得了重大进展。据我们所知，使用羧酰胺配体进行研究的最重要成果是柯林斯及其同事发现了四酰胺基大环配体（TAML），他们成功制造了7代的Fe-TAML催化剂，并找到了有趣的应用。