Electron-structure calculations and bond order analysis using density functional theory of cationic dinuclear arene ruthenium complexes.
Electron-structure calculations and bond order analysis using density functional theory of cationic dinuclear arene ruthenium complexes.
复制标题
使用阳离子双核芳烃钌络合物的密度泛函理论进行电子结构计算和键序分析。
作者：
E. P. Fowe;B. Therrien;G. Süss;C. Daul
阳离子配合物中金属-金属键相互作用的结构和性质[（η 6-C6Me6）2Ru2（μ 2-H）3]+（1），[（η 6-C6Me6）2Ru2（μ 2-H）2（mu2- 1，4-SC6H4Br）]+（2），[（η 6-C6Me6）2Ru2（μ 2-H）（μ 2 - 1，4-SC 6 H4 Br）2]+（3），和[（η 6-C6Me6）2Ru2在密度泛函理论（DFT）水平上，采用分子轨道（MO）理论、键级（BO）分析、键分解能（BDE）、电子定位函数（ELF）和密度方法的拉普拉斯算子。结果表明，在1-4中，两个钌原子之间没有直接的键，双钌骨架内的MO相互作用被桥连配体稳定。对于配合物1，ELF清楚地表明，双钌骨架内的键是通过三个桥接的氢化物配体，其作为一种胶，通过形成三中心的两电子键，其特征在于（Ru，H，Ru）盆地与1.8 e主要位于H原子盆地。
The structure and nature of the metal-metal bonding interaction in the cationic complexes [(eta6-C6Me6)2Ru2(mu2-H)3]+ (1), [(eta6-C6Me6)2Ru2(mu2-H)2(mu2-1,4-SC6H4Br)]+ (2), [(eta6-C6Me6)2Ru2(mu2-H)(mu2-1,4-SC6H4Br)2]+ (3), and [(eta6-C6Me6)2Ru2(mu2-1,4-SC6H4Br)3]+ (4) have been studied at the density functional theory (DFT) level using molecular orbital (MO) theory, bond order (BO) analysis, bond decomposition energy (BDE), electron localization function (ELF), and Laplacian of the density methods. The results show that there is no direct bond between the two ruthenium atoms in 1-4, the MO interaction within the diruthenium backbone being stabilized by the bridging ligands. For complex 1, the ELF clearly shows that the bond within the diruthenium backbone is through the three bridging hydride ligands, which act as a sort of glue by forming three-center two-electron bonds characterized by (Ru, H, Ru) basins with 1.8 e mostly located in the H atomic basin.