Structure and reversible pyran formation in molybdenum pyranopterin dithiolene models of the molybdenum cofactor.
Structure and reversible pyran formation in molybdenum pyranopterin dithiolene models of the molybdenum cofactor.
复制标题
钼辅因子的吡喃蝶呤二硫烯模型的结构和可逆吡喃形成。
DOI：
10.1021/ja310018e
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发表时间：
2012
影响因子：
15
通讯作者：
Burgmayer,SharonJNieter
中科院分区：
文献类型：
--
作者：
Williams,BenjaminR;Fu,Yichun;Yap,GlennPA;Burgmayer,SharonJNieter
报道了两种具有生物相关性的钼（4+）和钼（5+）态pyranopterin二硫烯配合物的合成及其x射线结构。晶体学表明，这些配合物具有一个吡喃环，是由蝶呤CN键上的二硫代侧链羟基自发环化反应形成的。Mo（4+）配合物的核磁共振数据表明，溶液中发生了可逆的吡喃环环化。这些结果为钼和钨酶中的蝶呤二硫代烯配体可以通过蛋白质调节的动态过程参与催化提供了实验证据。
The syntheses and X-ray structures of two molybdenum pyranopterin dithiolene complexes in biologically relevant Mo(4+) and Mo(5+) states are reported. Crystallography reveals that these complexes possess a pyran ring formed through a spontaneous cyclization reaction of a dithiolene side-chain hydroxyl group at a CN bond of the pterin. NMR data on the Mo(4+) complex suggest that a reversible pyran ring cyclization occurs in solution. These results provide experimental evidence that the pyranopterin dithiolene ligand in molybdenum and tungsten enzymes could participate in catalysis through dynamic processes modulated by the protein.