The Covalent Au(I)-Au(I) Bond in (AuF)(n) (n=2-4): A Perspective to Understand the Closed-Shell Au(I)...Au(I) Interaction
The Covalent Au(I)-Au(I) Bond in (AuF)(n) (n=2-4): A Perspective to Understand the Closed-Shell Au(I)...Au(I) Interaction
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(AuF)(n) (n=2-4) 中的共价 Au(I)-Au(I) 键：了解闭壳 Au(I)...Au(I) 相互作用的视角
DOI：
10.1021/acs.inorgchem.1c03151
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发表时间：
2022
影响因子：
4.6
通讯作者：
Cheng Longjiu
中科院分区：
文献类型：
--
作者：
Yu Xinlei;Li Dan;Wang Kun;Xia Tao;Xu Chang;Wu Zhenyu;Cheng Longjiu
封闭壳层AuI···AuI吸引的性质在理论化学中仍然是一个难题。而对于Z字形构象的Au 2F 2，AuF单体之间的d10-d10闭壳层相互作用表现为配位共价键。化学成键分析表明，强的AuI···AuI吸引力是由Au的异常活跃的5d轨道参与引起的。基于我们的研究，Au原子的5d轨道之一被激活，与它的6s和6p轨道杂化，形成杂化dsp 2轨道，其中每个Au原子在二聚化中既是电子供体（刘易斯碱）又是电子受体（刘易斯酸）。实际上，在Au_2X_2（X = F，Cl，Br，I，或NH_2）的Z字形构象中，闭壳层Au_I···Au_I相互作用是共价的。我们的结果提供了一个相当简单但明确的例子，其中神秘的AuI···AuI吸引力可能用共价键理论来解释。
The nature of closed-shell AuI···AuIattraction is still a conundrum in theoretical chemistry. However, for Au2F2with a zigzag conformation, the d10–d10closed-shell interaction between the AuF monomers is demonstrated as a coordinate covalent bond. Chemical bonding analysis reveals that the strong AuI···AuIattraction is caused by the participation of the extraordinary active 5d orbital of Au. Based on our study, one of the 5d orbitals of the Au atom is activated to hybridize with its 6s and 6p orbitals to form hybridized dsp2orbitals, where each Au atom is both an electron donor (Lewis base) and acceptor (Lewis Acid) in dimerization. Actually, the closed-shell AuI···AuIinteraction in the zigzag conformation of Au2X2(X = F, Cl, Br, I, or NH2) is covalent. Our results provide a rather simple but clear-cut example, where mysterious AuI···AuIattractions can be possibly explained by the covalent bond theory.