New Vistas in Porphyrinoid Chemistry: Corrolazine Synthesis and Reactivity

这个无机、生物无机和有机金属化学项目的研究奖支持约翰霍普金斯大学的David Goldberg教授对一种新的过渡金属卟啉类化合物的合成和反应性进行基础研究，这种化合物被称为腐蚀嗪。目前正在研究合成新的金属氯胺嘧啶的方法，重点是锰和铁配合物。为了稳定高氧化态，设计了氯嗪配体，目的是合成和表征高价金属-氧基团。金属铁和锰之所以被选择作为研究对象，是因为它们在合成催化剂以及血红素蛋白等生物相关环境中广泛使用。这些物质在氧原子转移和氢原子转移反应中的反应活性正在研究中。目前正在研究氯吡嗪配体对这些高价金属的稳定性和反应性的影响，以及辅助配体的作用。高价金属-氧配合物和相关的高氧化态物质在许多催化过程和生物系统中发挥着关键作用，包括血红素酶，但由于其固有的不稳定性，它们难以研究。该平台旨在提高其稳定性，并允许对其进行直接检测，从而提供对其光谱特性、反应性和作用机制的基本见解。通过参与这项基础研究，本科生、研究生和博士后水平的学生正在接受最先进的无机和生物无机化学方法的强化训练。他们正在获得成为独立科学家所必需的技能，例如在概念框架中制定和测试假设以及分析和解释实验数据。从这项研究中获得的知识将有助于设计用于工业过程的新型合成催化剂，并且该研究还将为生物相关的金属酶提供基础见解。

This research award in the Inorganic, Bioinorganic and Organometallic Chemistry Program supports work by Professor David Goldberg at Johns Hopkins University to carry out fundamental studies on the synthesis and reactivity of a new class of transition metal porphyrin-like compounds known as corrolazines. Methodology is being developed to synthesize new metallocorrolazines, focusing on manganese and iron complexes. The corrolazine ligand is designed to stabilize high oxidation states, and the synthesis and characterization of high-valent metal-oxo species are targeted. The metals iron and manganese have been selected for study because of their widespread use in synthetic catalysts as well as in biologically-relevant environments such as heme proteins. The reactivity of these species in oxygen-atom-transfer and hydrogen-atom-transfer reactions is under investigation. The influence of the corrolazine ligand on the stability and reactivity of these high-valent metal species is being examined, as well as the role of ancillary ligands. High-valent metal-oxo complexes and related high oxidation state species play key roles in a number of catalytic processes and biological systems, including heme enzymes, but they are difficult to study because of their inherent instability. The corrolazine platform is designed to increase their stability and allow for their direct examination, providing fundamental insights into their spectroscopic properties, reactivity, and mechanism of action.Through participation in this fundamental research, students at the undergraduate, graduate, and postdoctoral levels are receiving intensive training in state-of-the-art inorganic and bioinorganic chemical methods. They are gaining the skills necessary to become independent scientists, such as formulating and testing hypotheses and analyzing and interpreting experimental data in a conceptual framework. The knowledge gained from this research should help in the design of novel synthetic catalysts for industrial processes, and the research should also provide fundamental insights into biologically-relevant metalloenzymes.