Bulatova Margarita, Ivanov Daniil M, Rautiainen J Mikko, Kinzhalov Mikhail A, Truong Khai-Nghi, Lahtinen Manu, Haukka Matti
Department of Chemistry, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä, Finland.
Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, Russian Federation.
Inorg Chem. 2021 Sep 6;60(17):13200-13211. doi: 10.1021/acs.inorgchem.1c01591. Epub 2021 Aug 6.
Two isostructural -[MI(CNXyl)]·I (M = Pd or Pt; CNXyl = 2,6-dimethylphenyl isocyanide) metallopolymeric cocrystals containing uncommon bifurcated iodine···(metal-iodide) contact were obtained. In addition to classical halogen bonding, single-crystal X-ray diffraction analysis revealed a rare type of metal-involved stabilizing contact in both cocrystals. The nature of the noncovalent contact was studied computationally (via DFT, electrostatic surface potential, electron localization function, quantum theory of atoms in molecules, and noncovalent interactions plot methods). Studies confirmed that the I···I halogen bond is the strongest noncovalent interaction in the systems, followed by weaker I···M interaction. The electrophilic and nucleophilic nature of atoms participating in I···M interaction was studied with ED/ESP minima analysis. In -[PtI(CNXyl)]·I cocrystal, Pt atoms act as weak nucleophiles in I···Pt interaction. In the case of -[PdI(CNXyl)]·I cocrystal, electrophilic/nucleophilic roles of Pd and I are not clear, and thus the nature of the I···Pd interaction was suggested.
获得了两种等结构的 -[MI(CNXyl)]·I（M = Pd 或 Pt；CNXyl = 2,6 - 二甲基苯基异腈）金属聚合物共晶体，其中含有不常见的分叉碘···（金属 - 碘化物）接触。除了经典的卤键外，单晶 X 射线衍射分析表明两种共晶体中都存在一种罕见的涉及金属的稳定接触。通过计算（采用密度泛函理论、静电表面势、电子定位函数、分子中原子的量子理论和非共价相互作用绘图方法）研究了这种非共价接触的性质。研究证实，I···I 卤键是体系中最强的非共价相互作用，其次是较弱的 I···M 相互作用。通过 ED/ESP 极小值分析研究了参与 I···M 相互作用的原子的亲电和亲核性质。在 -[PtI(CNXyl)]·I 共晶体中，Pt 原子在 I···Pt 相互作用中充当弱亲核试剂。在 -[PdI(CNXyl)]·I 共晶体的情况下，Pd 和 I 的亲电/亲核作用不明确，因此提出了 I···Pd 相互作用的性质。
