New Vistas in Porphyrinoid Chemistry: Corrolazine Synthesis and Reactivity

无机化学、生物无机化学和金属有机化学项目的这项研究奖支持约翰霍普金斯大学的大卫·戈德伯格教授对一类新的过渡金属类似卟啉化合物的合成和反应性进行基础研究，该化合物被称为腐拉津。目前正在开发合成新的金属氮杂环化合物的方法，重点是锰和铁的络合物。腐拉津配体被设计用于稳定高氧化态，高价金属氧物种的合成和表征是目标。铁和锰这两种金属之所以被选为研究对象，是因为它们广泛用于合成催化剂以及与生物相关的环境中，如血红素蛋白质。这些物种在氧原子转移和氢原子转移反应中的反应性正在研究中。腐拉津配体对这些高价金属物种的稳定性和反应活性的影响以及辅助配体的作用正在被研究。高价金属氧络合物和相关的高氧化态物种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，对它们的研究很困难。腐拉津平台旨在增加它们的稳定性，并允许对它们进行直接检查，提供对它们的光谱性质、反应性和作用机理的基本见解。通过参与这一基础研究，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培训。他们正在获得成为独立科学家所需的技能，例如在概念框架中制定和测试假设，分析和解释实验数据。从这项研究中获得的知识应该有助于设计用于工业过程的新型合成催化剂，这项研究也应该为与生物相关的金属酶提供基本的见解。

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.