Restricted rotation of an Fe(CO)<sub>2</sub>(PL<sub>3</sub>)-subunit in [FeFe]-hydrogenase active site mimics by intramolecular ligation
作者:Sonja Pullen、Somnath Maji、Matthias Stein、Sascha Ott
DOI:10.1039/c8dt05148h
日期:——
demonstrated with the preparation of three novel complexes. A detailed theoretical investigation showes that by introducing a rigid covalent link between the phosphine and the bridging dithiolate ligands, the rotation of the Fe(CO)2P unit is hindered and higher rotation barriers were calculated compared to non-linked reference complexes. The concept of restricting Fe(L)3 rotation is an approach to kinetically
制备并表征了一系列新的同核铁络合物作为[FeFe]-加氢酶活性位点的模型。通式[Fe 2(mcbdt)(CO)5 PPh 2 R](mcbdt =苯-1,2-二硫醇-3-羧酸)的配合物具有将mcbdt配体与膦配体连接的共价链最终与Fe中心之一协调。通过制备三种新型配合物证明了该概念的综合可行性。详细的理论研究表明,通过在膦与桥连的二硫醇盐配体之间引入刚性的共价键,Fe(CO)2的旋转与未连接的参比络合物相比,P单位受阻,并且计算出更高的旋转势垒。限制Fe(L)3旋转的概念是一种动力学上稳定末端氢化物的方法,该末端氢化物是酶催化质子还原循环中的反应性中间体。