Abstract

The electron and structural understanding of metal-coordinated pentadienyl ligands is essential for their subsequent use in different areas of chemistry, especially in the area of organometallic chemistry. Thus, in this work we have analyzed in gas-phase the influence of group 17 elements in complexes formed with the lanthanum atom and the open pentadienyl ligand, XLa(C₅H₇)₂, where X = H, F, Cl, Br, and I. The results, using density functional theory (PBE0/def2-TZVP) and NBO analysis, suggest that all carbon atoms of both ligands are η⁵ coordinated to the lanthanum atom, and X atoms play a very important role in affecting the electron transfer from the ligands to the central atom due to their electronegativity. In addition, the NBO analysis and the geometry of each structure suggest that the atoms that contribute the most as charge donors to the lanthanum atom are those at the center of the pentadienyl ligand. Energies were computed with the domain based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) method.

Graphic abstract

中文翻译：

---

卤素对有机金属开放的戊二烯基镧配合物X La（C 5 H 7）2（X = H，F–I）的影响

摘要

对金属配位的戊二烯基配体的电子和结构理解对于其随后在化学的不同领域（尤其是在有机金属化学的领域）的后续使用至关重要。因此，在这项工作中，我们在气相中分析了与镧原子和开放的戊二烯基配体X La（C ₅ H ₇）₂形成的络合物中第17组元素的影响，其中X  = H，F，Cl， Br和I.结果，使用密度泛函理论（PBE0 / DEF2-TZVP）和NBO分析，表明，这两个配体的所有碳原子的η ⁵配位到镧原子，和X原子由于其电负性，在影响电子从配体到中心原子的转移中起着非常重要的作用。另外，NBO分析和每个结构的几何形状表明，作为镧原子电荷供体的贡献最大的原子是那些在戊二烯基配体中心的原子。使用基于域的局部对-自然轨道耦合簇（DLPNO-CCSD（T））方法计算能量。

图形摘要