金属-二氮-Keggin型多金属氧酸盐配合物的计算研究[PW 11 O 39 M II N 2 ]] 5–（M = Ru，Os，Re，Ir）：键合性质和二氮分裂,Inorganic Chemistry

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金属-二氮-Keggin型多金属氧酸盐配合物的计算研究[PW ₁₁ O ₃₉ M ^II N ₂ ]] ^5–（M = Ru，Os，Re，Ir）：键合性质和二氮分裂
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2015-08-04 00:00:00 , DOI: 10.1021/acs.inorgchem.5b01002
Chun-Guang Liu ₁ , Shuang Liu ₁ , Ting Zheng ₁

Affiliation

Keggin型多金属氧酸盐（POM）[PW ₁₁ O ₃₉ M ^II N ₂ ]的一系列金属-二氮衍生物的分子几何结构，电子结构和金属-二氮键键性质[ ⁵ ] （M = Ru，Os，Re， Ir）已通过使用具有M06L功能的密度泛函理论（DFT）方法进行了研究。在这些Keggin型POM配合物中，Os和Re-取代的POM配合物对N _2的吸附最为活跃，并具有相当大的吸附能。电子结构分析表明，锇^II和R e ^II在他们的金属-二氮POM络合物中心具有π ²_XZ π ²_YZπ ²_的xy和π ²_XZ π ²_YZ π ¹_的xy，配置分别。DFT-M06L计算表明，这项工作中针对Ru–，Os–和Re-dinitrogen POM配合物提出的可能的合成路线在各种溶剂环境下在热力学上都是可行的。同时，对Re-dinitrogen POM复合物进行了直接裂解二氮分子的评估。在反应机理中，a的二聚体Keggin型POM衍生物可以代表经历N–N键断裂的中间体。所计算出的自由能屏障（Δ ģ ^⧧用于与锯齿形态的过渡态）是16.05千卡摩尔^-1在四氢呋喃中，与文献值相比，它是N-N键断裂的适度屏障。总之，关于二氮分子的直接裂解，这一发现对于指导将潜在的N ₂裂解化合物搜索到完全无机的POM领域中非常有用。

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Computational Study of Metal–Dinitrogen Keggin-Type Polyoxometalate Complexes [PW11O39MIIN2)]5– (M = Ru, Os, Re, Ir): Bonding Nature and Dinitrogen Splitting

Molecular geometry, electronic structure, and metal–dinitrogen bonding nature of a series of metal–dinitrogen derivatives of Keggin-type polyoxometalates (POMs) [PW₁₁O₃₉M^IIN₂)]^5– (M = Ru, Os, Re, Ir) have been studied by using a density functional theory (DFT) method with the M06L functional. Among these Keggin-type POM complexes, Os- and Re-substituted POM complexes are the most active for N₂ adsorption with considerable adsorption energy. The electronic structure analysis shows that Os^II and Re^II centers in their metal–dinitrogen POM complexes possess π²_xzπ²_yzπ²_xy and π²_xzπ²_yzπ¹_xy configurations, respectively. DFT-M06L calculations show that the possible synthesis routes proposed in this work for the Ru–, Os–, and Re–dinitrogen POM complexes are thermodynamically feasible under various solvent environments. Meanwhile, the Re–dinitrogen POM complex was assessed for the direct cleavage of dinitrogen molecule. In the reaction mechanism, a dimeric Keggin-type POM derivative of rhenium could represent the intermediate which undergoes N–N bond scission. The calculated free energy barrier (ΔG^⧧) for a transition state with a zigzag conformation is 16.05 kcal mol^–1 in tetrahydrofuran, which is a moderate barrier for the cleavage of the N–N bond when compared with the literature values. In conclusion, regarding the direct cleavage of the dinitrogen molecule, the findings would be very useful to guide the search for a potential N₂ cleavage compound into totally inorganic POM fields.

更新日期：2015-08-04

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