An ab initio study on coinage atom-inserted cyanide/isocyanide: XMCN/XMNC (M = coinage atoms; X = halogen)†,RSC Advances

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An ab initio study on coinage atom-inserted cyanide/isocyanide: XMCN/XMNC (M = coinage atoms; X = halogen)†
RSC Advances ( IF 3.9 ) Pub Date : 2018-04-18 00:00:00 , DOI: 10.1039/c8ra00397a
Zhengguo Huang ₁ , Xiaohong Wang ₁ , Jingbo Zhang ₁ , Yuqing Li ₁ , Yuying Li ₁

Affiliation

The coinage atom-inserted cyanide/isocyanide compounds, XMCN and XMNC (X = halogens) formed by the insertion of a coinage atom into the X–C(N) bonds of XCN (or XNC), were investigated by ab initio methods. XMCN was predicted to be more stable than XMNC, which is different from the case of XUCN/XUNC reported previously. Based on the analyses on the ionization dissociation pathways, the M–C (or M–N) bond is more easily broken than the X–M bond. Moreover, the order of the M–C (or M–N) bond energy in XMCN (or XMNC) is XAuCN (XAuNC) > XCuCN (XCuNC) > XAgCN (XAgNC). The shift characters of v_C–N in XMCN (or XMNC) with respect to the concerning precursor can be used to identified XMCN and XMNC experimentally. The results of charge decomposition analysis (CDA) and atoms-in-molecule (AIM) illustrate that the X–M and M–C(N) bond behaves as a coordination bond, while the C–N bond is a typical polar covalent bond. The higher thermodynamic stability of XMCN is the result of the –CN group having better coordination ability than the –NC group.

中文翻译：

关于插入造币原子的氰化物/异氰化物的从头算研究：XMCN/XMNC（M = 造币原子；X = 卤素）†

通过从头计算方法研究了通过将造币原子插入 XCN（或 XNC）的 X-C(N) 键而形成的造币原子插入氰化物/异氰化物化合物 XMCN 和 XMNC（X = 卤素）。预计 XMCN 比 XMNC 更稳定，这与之前报道的 XUCN/XUNC 的情况不同。根据电离解离途径的分析，M-C（或M-N）键比X-M键更容易断裂。此外，XMCN（或XMNC）中M-C（或M-N）键能的顺序为XAuCN（XAuNC）> XCuCN（XCuNC）> XAgCN（XAgNC）。XMCN（或 XMNC）中v _C-N相对于相关前体的位移特征可用于通过实验来识别 XMCN 和 XMNC。电荷分解分析(CDA)和分子内原子(AIM)的结果表明X-M和M-C(N)键表现为配位键，而C-N键是典型的极性共价键。XMCN较高的热力学稳定性是由于-CN基团比-NC基团具有更好的配位能力的结果。

更新日期：2018-04-18

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