Theoretical Study on Reaction Scheme of Silver(I) Containing 5-Substituted Uracils Bridge Formation
Theoretical Study on Reaction Scheme of Silver(I) Containing 5-Substituted Uracils Bridge Formation
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含5位取代尿嘧啶桥的银(I)反应方案的理论研究
DOI：
10.1021/jp200871f
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发表时间：
2011
影响因子：
2.9
通讯作者：
重田育照
中科院分区：
文献类型：
--
作者：
松井亨;宮地秀明;馬場剛史;重田育照
利用类导体极化连续模型（CPCM）-B3 LYP/aug-cc-pVDZ水平，提出了含银的5-取代尿嘧啶（N）与两个银离子形成银介导的碱基对[N-Ag 2-N]的反应方案.整个反应流程分为以下三个步骤：（1）银离子结合和去质子化，（2）银离子转移，（3）二聚体形成和结构波动。用我们以前提出的一种新的pK计算方案，发现一个银配位使N的pK降低了2.5-3.0 pK单位，这是N对银离子选择性的一个重要线索。计算结果表明，银离子转移反应和二聚反应是自发进行的。此外，这两个反应是独立的C5配体在N，所以去质子化反应，这是该方案的第一步，在形成[N-Ag 2-N]配对中起着关键作用。
We present a reaction scheme of silver containing 5-substituted uracils (N) bridge formation with two silver ions to a silver-mediated base pair [N-Ag2-N] by using the conductor-like polarizable continuum model (CPCM)-B3LYP/aug-cc-pVDZ level of theory. The whole reaction scheme is divided into the following three steps: (1) silver ion binding and deprotonation, (2) silver ion transfer, and (3) dimer formation and structural fluctuation. With a new pKacomputing scheme proposed in our previous studies, it is found that a silver coordination decreases the pKaofNby 2.5–3.0 pKaunits, which is an important clue for silver-ion selectivity byN. Judging from the calculation, we revealed that the silver ion transfer reaction and the dimerization reaction occur spontaneously. Moreover, both reactions are independent of the C5 ligand inNso that the deprotonation reaction, which is the first step of this scheme, plays a key role in forming the [N-Ag2-N] pairing.