New Vistas in Porphyrinoid Chemistry: Corrolazine Synthesis and Reactivity

这项研究奖在无机，生物无机和有机化学计划支持教授大卫戈德堡在约翰霍普金斯大学的工作进行基础研究的合成和一类新的过渡金属卟啉类化合物的反应性称为corrolazines。目前正在开发合成新的金属环唑啉的方法，重点是锰和铁的络合物。设计了corrolazine配体以稳定高氧化态，并且针对高价金属-氧代物种的合成和表征。金属铁和锰已被选择用于研究，因为它们广泛用于合成催化剂以及生物相关的环境，如血红素蛋白。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。 这些高价金属物种的稳定性和反应性的corrolazine配体的影响正在检查，以及辅助配体的作用。高价金属-氧代配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起着关键作用，包括血红素酶，但由于其固有的不稳定性，它们很难研究。corrolazine平台旨在提高其稳定性，并允许对其进行直接检查，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培训。他们正在获得成为独立科学家所需的技能，例如制定和测试假设，并在概念框架中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，这项研究还应该为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.