含硫过渡金属基元的反应 2: 双膦及双齿巯基混合配位钴, 镍化合物的合成和结构特征

双膦(P-P)和1, 2-双齿巯基(S-X)混合与MCl2(M=Co, Ni)反应,得到通式为M(S-X)(P-P)的产物。晶体结构测定表明, 配合物Co(bdt)(dppe)(1), Ni(tdt)(dppm)(2)和Ni(tsal)(dppe)(3)中的金属均为SXP2配位的四方平面构型, S, X, P原子分别来自二种双齿配体, 各形成四、五或六元螯合配位环。文中总结了结构特征, 探讨了基元配合物稳定的原因。     

Chiral metal cluster and nanocluster complexes and their application in asymmetric catalysis

Asymmetric catalysis has always been the focus of attention for synthetic chemistry. In this review, we summarize recent advances in the synthesis and asymmetric catalysis application of chiral metal clusters, nanoclusters and nanoparticles.     

Hybrid organic–inorganic CH3NH3PbI3 perovskite building blocks: Revealing ultra‐strong hydrogen bonding and mulliken inner complexes and their implications in materials design

Methylammonium lead iodide (CH₃NH₃PbI₃) perovskite compound has produced a remarkable breakthrough in the photovoltaic history of solar cell technology because of its outstanding device‐based performance as a light‐harvesting semiconductor. Whereas the experimental and theoretical studies of this system in the solid state have been numerously reported in the last 4 years, its fundamental cluster physics is yet to be exploited. To this end, this study has performed theoretical investigations using DFT‐M06‐2X/ADZP to examine the principal geometrical, electronic, topological, and orbital properties of the CH₃NH₃PbI₃ molecular building block. The intermolecular hydrogen bonded interactions examined for the most important conformers of the system are found to be unusually strong, with binding energies lying between −93.53 and −125.11 kcal mol⁻¹ (beyond the covalent limit, −40 kcal mol⁻¹), enabling us to classify the underlying interactions as ultra‐strong type since their characteristic properties are unidentical with those have already been proposed as very strong, strong, moderate, weak, and van der Waals. Based on this, together with the unusually high charge transfers, strong hyperconjugative interactions, sophisticated topologies of the charge density, and short intermolecular distances of separation, we have characterized the conformers of CH₃NH₃PbI₃ as Mulliken inner complexes. The consequences of these, as well as of the ultra‐strong interactions, in designing novel functional nanomaterials are outlined. © 2017 Wiley Periodicals, Inc.