π配位吡咯碳如何加氢

DJ_Tokyo

π配位吡咯碳如何加氢

案例来源：CCDC[1] 1993060. Inorg.Chem. Commun. 2020, 119, 108036. DOI[2]:10.1016/j.inoche.2020.108036.

案例结构如图1所示（由ChemBioDraw[3]绘制）。

▲图1 案例结构

当吡咯环与金属以η5-模式与金属形成π→M键时，其碳原子除了2个C‒C键之外还有1个M‒C键（本例中为Er‒C键），因此直接进行理论加氢时，程序会将其当作次甲基碳从而给它加1个AFIX代码为13的氢（参阅推文“SHELXL指令之AFIX”），如图2所示（由Olex2[4]呈现）。

▲图2 碳原子上加错氢

对于这种情况，有2种处理方法，其一是使用SHELXL[5]指令FREE（参阅推文“SHELXL指令之FREE”）暂时将其中远端的Er‒C键删除（delete键删除的方式无效），如图3所示。

▲图3 删除Er‒C键

此时对这两个碳进行理论加氢，则加上正确的AFIX代码为43的两个氢，如图4所示。

▲图4 加氢

然后再把ins文件中删除Er‒C键的FREE指令移除从而恢复Er‒C键，如图5所示。

▲图5 恢复Er‒C键

然后正常精修即可。

第二种方法，在Olex2中可以按下快捷组合键“Ctrl+Shift+/”使得配体和金属之间之间的键暂时断开，如图6所示。

▲图6 断开金属与配体之间的键

此时对这两个碳进行理论加氢，则加上正确的AFIX代码为43的两个氢，如图7所示。

▲图7 加氢

然后按下快捷组合键“Ctrl+/”恢复配体和金属之间的键，如图8所示。

▲图8 恢复配体和金属之间的键

然后正常精修即可。

视频操作演示请参阅：

π配位吡咯碳如何加氢：https://www.bilibili.com/video/BV1SPfZYaEND

参考文献

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