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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Noncovalent interactions of Cu+ with N-donor ligands (pyridine, 4,4-dipyridyl, 2,2-dipyridyl, and 1,10-phenanthroline): Collision-induced dissociation and theoretical studies
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Noncovalent interactions of Cu+ with N-donor ligands (pyridine, 4,4-dipyridyl, 2,2-dipyridyl, and 1,10-phenanthroline): Collision-induced dissociation and theoretical studies

机译：Cu +与N-供体配体（吡啶，4,4-二吡啶基，2,2-二吡啶基和1,10-菲咯啉）的非共价相互作用：碰撞诱导的解离和理论研究

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Collision-induced dissociation of complexes of Cu+ bound to a variety of N-donor ligands (N-L) with Xe is studied using guided ion beam tandem mass spectrometry. The N-L ligands examined include pyridine, 4,4-dipyridyl, 2,2-dipyridyl, and 1,10-phenanthroline. In all cases, the primary and lowest-energy dissociation channel observed corresponds to the endothermic loss of a single intact N-L ligand. Sequential dissociation of additional N-L ligands is observed at elevated energies for the pyridine and 4,4-dipyridyl complexes containing more than one ligand. Ligand exchange processes to produce Cu+Xe are also observed as minor reaction pathways in several systems. The primary cross section thresholds are interpreted to yield 0 and 298 K bond dissociation energies (BDEs) after accounting for the effects of multiple ion-neutral collisions, the kinetic and internal energy distributions of the reactants, and dissociation lifetimes. Density functional theory calculations at the B3LYP/6-31G* level are performed to obtain model structures, vibrational frequencies, and rotational constants for the neutral N-L ligands and the Cu+(N-L)(x) complexes. The relative stabilities of the various conformations of these N-L ligands and Cu+(N-L)(x) complexes as well as theoretical BDEs are determined from single point energy calculations at the B3LYP/6-311+G(2d,2p) level of theory using B3LYP/6-31G* optimized geometries. Excellent agreement between theory and experiment is observed for all complexes containing one or two N-L ligands, while theory systematically underestimates the strength of binding for complexes containing more than two N-L ligands. The ground-state structures of these complexes and the trends in the sequential BDEs are explained in terms of stabilization gained from sd-hybridization and repulsive ligand-ligand interactions. The nature of the binding interactions in the Cu+(N-L)(x) complexes are examined via natural bond orbital analyses.
机译：使用引导离子束串联质谱技术研究了碰撞导致的与Xe结合的多种N-供体配体（N-L）的Cu +配合物的解离。检查的N-L配体包括吡啶，4，4-二吡啶基，2，2-二吡啶基和1，10-菲咯啉。在所有情况下，观察到的主要和最低能量解离通道对应于单个完整N-L配体的吸热损失。对于含有多个配体的吡啶和4,4-二吡啶基配合物，在升高的能量下观察到了其他N-L配体的顺序解离。在几个系统中，作为次要的反应途径，也观察到产生Cu + Xe的配体交换过程。在考虑了多次离子中性碰撞，反应物的动能和内能分布以及离解寿命之后，将主要横截面阈值解释为产生0和298 K的键离解能（BDE）。执行B3LYP / 6-31G *级别的密度泛函理论计算以获得中性N-L配体和Cu +（N-L）（x）配合物的模型结构，振动频率和旋转常数。这些NL配体和Cu +（NL）（x）配合物以及理论BDE的各种构象的相对稳定性是根据B3LYP / 6-311 + G（2d，2p）的理论上的单点能量计算确定的B3LYP / 6-31G *优化的几何形状。对于包含一个或两个N-L配体的所有复合物，理论与实验之间均观察到极好的一致性，而理论上系统地低估了包含两个以上N-L配体的复合物的结合强度。这些复合物的基态结构和连续BDE的趋势是通过sd杂交和排斥性配体-配体相互作用获得的稳定性来解释的。通过自然键轨道分析来检查Cu +（N-L）（x）配合物中结合相互作用的性质。

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