Multiple d-d bonds between early transition metals in TM2Lin(TM = Sc, Ti) superatomic molecule clusters
Multiple d-d bonds between early transition metals in TM2Lin(TM = Sc, Ti) superatomic molecule clusters
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TM2Lin(TM = Sc, Ti) 超原子分子簇中早期过渡金属之间的多个 d-d 键
DOI：
10.1039/d0nr05480a
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发表时间：
2020
期刊：
影响因子：
6.7
通讯作者：
Cheng Longjiu
中科院分区：
文献类型：
--
作者：
Zhou Yichun;Yu Xinlei;Cheng Longjiu
Cr-Cr和V-V d-d五重键（σ，2π，2δ）化合物的合成和应用，使人们对Sc-Sc和Ti-Ti等早期过渡金属之间是否也存在d-d重键产生了新的思考。本研究在密度泛函理论水平上，通过广泛的无偏全局搜索，得到了26 e和30 e TM 2Lin团簇的低能结构.基于超价键（SVB）理论，将TM 2Lin团簇的长形双核结构视为一个超原子分子，将其每一半视为一个开壳层超原子，通过超原子间形成多键实现电子壳层闭合.然后，通过化学键分析确认了Li 18 Ti 2、Li 20 Sc2、[Li 17 V2]+、[Li 17 Ti 2]-簇的五重超键（2δ，2π，σ）以及Li 24 Sc2和Li 24 Y2簇的三重超键（2π，σ）。这种通过超原子成键在前过渡金属之间形成多重键的方式，促进了前过渡金属多重键化合物的实验合成和应用。
The synthesis and application of compounds with Cr–Cr and V–V d–d quintuple bonds (σ, 2π, 2δ) have led to new thinking about whether d–d multiple bonds also exist between early transition metals such as Sc–Sc and Ti–Ti. In this study, by extensive unbiased global search at the density functional theory level, the low-energy structures of 26e and 30e TM2Lin clusters were obtained. Based on the super valence bond (SVB) theory, the prolate double-core structure of TM2Lin clusters was regarded as a superatomic molecule, of which each half was regarded as an open-shell superatom, and the electronic shell-closure was realized by forming multiple bonds between superatoms. Then, the quintuple super bonds (2δ, 2π, σ) of the Li18Ti2, Li20Sc2, [Li17V2]+, [Li17Ti2]− clusters and the triple super bonds (2π, σ) of the Li24Sc2 and Li24Y2 clusters were confirmed via chemical-bonding analysis. This way of forming multiple bonds between early transition metals through superatomic bonding has promoted the experimental synthesis and application of early transition metal multiple bond compounds.