A Katkova Svetlana, S Mikherdov Alexander, A Kinzhalov Mikhail, S Novikov Alexander, A Zolotarev Andrey, Boyarskiy Vadim P, Kukushkin Vadim Yu
Saint Petersburg State University, Universitetskaya Nab., 7/9, Saint Petersburg, Russian Federation.
Chemistry. 2019 Jun 26;25(36):8590-8598. doi: 10.1002/chem.201901187. Epub 2019 May 30.
Inspection of the X-ray structures of the newly prepared trans-[M (CNXyl) (DAPT) ]Cl(BF ) (M=Pd, Pt; Xyl=2,6-Me C H ; DAPT=4,6-diaminopyrimidine-2(1H)-thione) complexes and the appropriate Hirshfeld molecular surface analysis allowed the recognition of the previously unknown π-hole⋅⋅⋅metal interactions between a ligated isocyano group (acting as a π-hole donor) and the positively charged d -Pt and d -Pd metal centers (acting as nucleophiles); this is the first identification of π-hole⋅⋅⋅metal interactions with triple-bond species. Results of DFT calculations followed by the topological analysis of the electron density distribution within the framework of Bader's theory (quantum theory of atoms in molecules, QTAIM) confirmed the presence of these contacts. The electrostatic surface potential calculations indicated that π-hole⋅⋅⋅metal contacts are formed upon interaction between the electrophilic isocyano C atom (π-hole donor) and the nucleophilic d orbital of the metal centers, which act as π-hole acceptors. Available CCDC data were processed from the perspective of the π-hole⋅⋅⋅metal interactions with isocyanide ligands, and their analysis disclosed the role of metal nucleophilicity in the corresponding π-hole acceptor ability.
对新制备的反式-[M(CNXyl)(DAPT)]Cl(BF )（M = Pd、Pt；Xyl = 2,6-Me C H ；DAPT = 4,6-二氨基嘧啶-2(1H)-硫酮）配合物的X射线结构进行检查，并进行适当的赫希菲尔德分子表面分析，使得能够识别出此前未知的π-空穴⋅⋅⋅金属相互作用，该相互作用存在于一个配位异氰基（作为π-空穴供体）与带正电荷的d -Pt和d -Pd金属中心（作为亲核试剂）之间；这是首次鉴定出与三键物种的π-空穴⋅⋅⋅金属相互作用。在Bader理论（分子中的原子量子理论，QTAIM）框架内对电子密度分布进行拓扑分析的DFT计算结果证实了这些接触的存在。静电表面势计算表明，π-空穴⋅⋅⋅金属接触是在亲电异氰基C原子（π-空穴供体）与作为π-空穴受体的金属中心的亲核d 轨道之间相互作用时形成的。从与异氰化物配体的π-空穴⋅⋅⋅金属相互作用的角度处理了现有的剑桥晶体学数据中心（CCDC）数据，其分析揭示了金属亲核性在相应π-空穴受体能力中的作用。
