Energy Materials Laboratory, School of Chemistry, University of East Anglia, Norwich Research Park, Norwich, NR4 7TJ, UK.
Dalton Trans. 2013 Jun 14;42(22):8140-6. doi: 10.1039/c3dt50642h. Epub 2013 Apr 17.
The active site of the [Fe]-hydrogenase features an iron(II) centre bearing cis carbonyl groups and a chelating pyridine-acyl ligand. Reproducing these unusual features in synthetic models is an intriguing challenge, which will allow both better understanding of the enzymatic system and more fundamental insight into the coordination modes of iron. By using the carbamoyl group as a surrogate for acyl, we have been able to synthesize a range of ferracyclic complexes. Initial reaction of Fe(CO)4Br2 with 2-aminopyridine yields a complex bearing a labile solvent molecule, which can be replaced by stronger donors bearing phosphorus atoms to produce a number of derivatives. Introduction of a hydroxy group using this method is unsuccessful both with a free OH group and when this is silyl-protected. In contrast, the analogous reactions starting from 2,6-diaminopyridine does allow synthesis of complexes bearing a pendant basic group.
[Fe]-氢化酶的活性部位具有一个铁(II)中心，带有顺式羰基和螯合吡啶酰基配体。在合成模型中重现这些不寻常的特征是一个有趣的挑战，这将使人们更好地了解酶系统，并更深入地了解铁的配位模式。通过使用氨甲酰基作为酰基的替代物，我们已经能够合成一系列的铁环状配合物。Fe(CO)4Br2 与 2-氨基吡啶的初始反应生成一个带有不稳定溶剂分子的配合物，该分子可以被带有磷原子的更强供体取代，生成多种衍生物。使用这种方法引入羟基，无论是带有游离 OH 基团还是硅基保护的 OH 基团，都不成功。相比之下，从 2,6-二氨基吡啶开始的类似反应确实允许合成带有侧基碱性基团的配合物。
