Huang Zhengguo, Wang Xiaohong, Zhang Jingbo, Li Yuqing, Li Yuying
Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic-Organic Hybrid Functional Materials Chemistry (Tianjin Normal University), Ministry of Education, College of Chemistry, Tianjin Normal University Tianjin 300387 People's Republic of China
RSC Adv. 2018 Apr 18;8(26):14705-14712. doi: 10.1039/c8ra00397a. eCollection 2018 Apr 17.
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 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 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.
通过相关方法对由货币金属原子插入XCN（或XNC）的X-C（N）键中形成的货币金属原子插入的氰化物/异氰化物化合物XMCN和XMNC（X =卤素）进行了研究。预测XMCN比XMNC更稳定，这与先前报道的XUCN/XUNC的情况不同。基于对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）中相对于相关前体的[具体内容缺失]的位移特征可用于通过实验鉴定XMCN和XMNC。电荷分解分析（CDA）和分子中的原子（AIM）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。
