水分子(簇)和水溶剂对脯氨酸铜(Ⅱ)对映异构的影响  

The effect of water molecule(cluster)and aqueous solvent on proline copper(Ⅱ) enantiomerization

作　　者：刘芳[1] 辛志荣 范艳洁 李心雨 潘宇[1] 杨清荟 姜春旭 王佐成[1] LIU Fang;XIN Zhirong;FAN Yanjie;LI Xinyu;PAN Yu;YANG Qinghui;JIANG Chunxu;WANG Zuocheng(College of Physics,Baicheng Normal University,Baicheng 137000,China)

机构地区：[1]白城师范学院物理学院,吉林白城137000

出　　处：《中山大学学报（自然科学版）（中英文）》2022年第5期105-116,共12页Acta Scientiarum Naturalium Universitatis Sunyatseni

基　　金：吉林省教育厅科学研究项目(JJKH20200002KJ);全国大学生创新项目(202010206014);吉林省自然科学基金(20130101131JC)。

摘　　要：采用密度泛函理论的M06和MN15方法,结合自洽反应场理论的SMD模型方法,研究了水分子(簇)和水溶剂对气相S-脯氨酸二价铜配合物(S-Pro·Cu(Ⅱ))对映异构的影响。研究发现:S-Pro·Cu(Ⅱ)的对映异构可在5个通道a、b、c、d和e实现,a、b和c通道分别是α-H直接以O、Cu、N为桥迁移;c和d通道是Cu与羰基O双齿配位后,α-H以O为桥以及O和N联合为桥迁移(其中α-H以Cu为桥迁移是氢负离子迁移,其他为氢质子迁移)。势能面计算表明:孤立的S-Pro·Cu(Ⅱ)在b和c通道的对映异构有明显的优势,反应活化能分别是153.4和160.3 kJ·mol^(−1)。水汽环境下c通道最具优势,反应活化能是143.7 kJ·mol^(−1),b通道最具劣势,在该通道的对映异构不能实现。水溶剂效应使c通道的反应活化能降到89.9 kJ·mol^(−1)。结果表明:脯氨酸铜(Ⅱ)在气相和水汽相下可以保持其手性特征,在水液相下容易对映异构。The study investigated the effect of water molecule(cluster)and aqueous solvent on S-proline(Pro)divalent copper complex(S-Pro·Cu(II))enantiomerization under the gas phase using the methods of M06 and MN15 based on density functional theory combining with self-consistent reaction field of SMD model.The results showed that gas phase Cu2+and carbonyl O monodentate ligand is the most stable.The enantiomerization of S-Pro·Cu(Ⅱ)can be realized in 5 channels a,b,c,d and e.In channel a,b and cα-H transfers directly with O,Cu and N as a bridge respectively.After Cu and carbonyl O are bidentately coordinatedα-H transfers with O and O and N unite as a bridge in channel c and d(α-H transfers with Cu as a bridge,it is hydrogen anion migration.The other is hydrogen proton migration).The potential energy surface calculation shows that the dominant pathways of the enantiomerization of isolated S-Pro·Cu(Ⅱ)are pathways b and c,and the activation energy of the reaction is 153.4 and 160.3 kJ·mol^(−1) respectively.The dominant pathway is channel c in the water vapor phase environment,and the activation energy of the reaction is 143.7 kJ·mol^(−1).Channel b is the most disadvantaged,and the enantiomerization in this channel cannot be achieved.The activation energy of channel c drops to 89.9 kJ·mol^(−1) under the effect of aqueous solvent.The results show that Pro·Cu(Ⅱ)can maintain its chiral characteristics well in the gas phase,and is easy to be enantiomerized in the water vapor phase.

关 键 词：脯氨酸 二价铜离子 水分子(簇) 水溶剂 对映异构 密度泛函理论 过渡态 能垒 

分 类 号：O641.12[理学—物理化学]