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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Investigation of the Coordination of N_2 Ligands to the Cluster Ni
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Theoretical Investigation of the Coordination of N_2 Ligands to the Cluster Ni

机译：N_2配体与Ni团簇配位的理论研究

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Various structures of complexes of the cluster Ni_3 with 3 to 12 N_2 ligands were modeled with a gradient-corrected density functional method.The stability of different types of bonding was considered and the most stable structures of Ni_3(N_2)_Xcomplexes(X= 3-9,12)were determined for neutral,cationic,and anionic systems.For the most stable structure of the neutral compleXwith three and siXN_2 ligands,we calculated average ligand binding energies of 116 and 98 kJ/mol,respectively;the binding energy per ligand decreases with increasing number of ligand molecules.For canonical ensembles of mono-and trinuclear complexes with N2 ligands at varying molar ratio k = [N_2]:[Ni_3],our results suggest that,in agreement with experiment,the compleXNi3(N2)6 is among the dominating species at saturation;yet,at sufficiently large molar ratios k,the trinuclear compleXwith seven ligands,not observed in experiment,also plays an important role in the simulated distributions.It is unclear whether this partial discrepancy in the product distribution originates from complications to simulate the experimental situation or from some aspects of the experimental procedure.Coordination of more than seven N_2 ligands is predicted to lead to a partial or full destruction of the Ni_3 moieties into mononuclear N_2 ligated complexes.The type of bonding of the N_2 ligands(end-on,side-on,hapticity)was found to affect the characteristics of the complexes,e.g.the binding energy,the charge of the Ni_3 moiety,and the activation of the ligands.End-on coordination of N_2 molecules to a Ni atom of the Ni_3 unit entails the most stable type of bonding,whereas side-on coordination causes a stronger elongation of N-N bonds.The ionization potential and the electron affinity of a Ni_3 cluster were calculated to increase after association of ligands.
机译：用梯度校正的密度泛函方法对Ni_3簇中具有3至12个N_2配体的配合物的各种结构进行建模，考虑了不同类型键合的稳定性，并获得了最稳定的Ni_3（N_2）_X配合物（X = 3-确定了9,12）的中性，阳离子和阴离子体系。对于具有三个和siXN_2配体的中性化合物的最稳定结构，我们分别计算出116和98 kJ / mol的平均配体结合能;每个配体的结合能随配体分子数目的增加而减少。对于具有不同摩尔比k = [N_2]：[Ni_3]的具有N2配体的单核和三核配合物的典范集合，我们的结果表明，与实验一致，compleXNi3（N2）6是饱和状态下的主要物种之一;然而，在足够大的摩尔比k时，实验中未观察到的具有七个配体的三核化合物在模拟分布中也起着重要作用。产品分布的差异主要源于模拟实验情况的复杂性或实验程序的某些方面。预计七个以上N_2配体的配位会导致Ni_3部分或部分破坏成单核N_2连接的复合物。发现N_2配体的键合类型（端对端，侧对面，触觉）会影响复合物的特性，例如结合能，Ni_3部分的电荷以及配体的活化。 N_2分子与Ni_3单元的Ni原子的配位关系是最稳定的键合类型，而侧向配位则使NN键的延伸更强。计算出Ni_3团簇的电离势和电子亲和力在配体缔合。

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