Priola Emanuele, Giordana Alessia, Gomila Rosa M, Zangrando Ennio, Andreo Luca, Rabezzana Roberto, Operti Lorenza, Diana Eliano, Mahmoudi Ghodrat, Frontera Antonio
Department of Chemistry, University of Turin, via P. Giuria 7, 10125 Torino, Italy.
Departament de Química, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122 Palma de Mallorca, Baleares, Spain.
Dalton Trans. 2022 Apr 12;51(15):5818-5827. doi: 10.1039/d2dt00615d.
This manuscript reports four new gold(I)-silver(I) complexes with 2-(2-pyridyl)-1,8-naphthyridine (pyNP) and terpyridine (terpy) as ancillary ligands, having formulae [Ag(pyNP)(Au(CN))] (1), [AgAu(μ-CN)(CN)(pyNP)] (2), [AgAu(μ-CN)(terpy)][Au(CN)] (3) and [AgAu(μ-CN)(terpy)(py)] (4). Complexes 1 and 2 are structural isomers obtained from different solvents. The Au(CN) anion is not coordinated and establishes intramolecular Au⋯Ag,Ag interactions in 1. In contrast, it is monocoordinated to silver atoms a CN fragment in compound 2 and no metallophilic interaction is observed. In compound 3, one Au(CN) anion bridges two Ag(terpy) fragments. In this complex an infinite array of gold atoms is found, exhibiting aurophilic interactions of 3.415 Å. In complex 4 the 3D architecture observed in the crystal packing is driven by Au⋯Au and Au⋯Ag metallophilic interactions. All compounds have been structurally and vibrationally characterized to better understand the crystal forces. In addition, a solution chemistry study in different solvents by ESI-MS spectrometry was performed to comprehend the speciation and solvent effects. Finally, DFT calculations were carried out to analyze the Ag⋯Au interactions and also the π-stacking interactions that are relevant in the crystal packing of some structures. Special attention has been paid to the bifurcated nature of the Au⋯Ag,Ag interactions in compound 1 that has been analyzed theoretically using the quantum theory of atoms-in-molecules (QTAIM) and the Natural Bond Orbital (NBO) computational tools.
本手稿报道了四种新的金（I）-银（I）配合物，它们以2-（2-吡啶基）-1,8-萘啶（pyNP）和三联吡啶（terpy）作为辅助配体，其化学式分别为[Ag(pyNP)(Au(CN))]（1）、[AgAu(μ-CN)(CN)(pyNP)]（2）、[AgAu(μ-CN)(terpy)][Au(CN)]（3）和[AgAu(μ-CN)(terpy)(py)]（4）。配合物1和2是由不同溶剂得到的结构异构体。Au(CN)阴离子未配位，在1中形成分子内Au⋯Ag、Ag相互作用。相比之下，在化合物2中它通过一个CN片段单配位到银原子上，未观察到亲金属相互作用。在化合物3中，一个Au(CN)阴离子桥连两个Ag(terpy)片段。在该配合物中发现了一个无限的金原子阵列，表现出3.415 Å的亲金相互作用。在配合物4中，晶体堆积中观察到的三维结构是由Au⋯Au和Au⋯Ag亲金属相互作用驱动的。所有化合物都通过结构和振动表征，以更好地理解晶体作用力。此外，通过电喷雾电离质谱法在不同溶剂中进行了溶液化学研究，以了解物种形成和溶剂效应。最后，进行了密度泛函理论计算，以分析Ag⋯Au相互作用以及一些结构晶体堆积中相关的π堆积相互作用。特别关注了化合物1中Au⋯Ag、Ag相互作用的分叉性质，已使用分子中的原子量子理论（QTAIM）和自然键轨道（NBO）计算工具对其进行了理论分析。
