On the Nature of the Bonding in Metal-Silane sigma-Complexes
G. Sean McGrady, Peter Sirsch, Nicholas P. Chatterton, Andreas Ostermann, Carlo Gatti, Sandra Altmannshofer, Verena Herz, Georg Eickerling, Wolfgang Scherer
The nature of metal silane sigma-bond interaction has been investigated in several key systems by a range of experimental and computational techniques. The structure of [Cp'Mn(CO)2(eta2-HSiHPh2)] 1 has been determined by single crystal neutron diffraction, and the geometry at the Si atom is shown to approximate to a trigonal bipyramid. This complex is similar to [Cp'Mn(CO)2(eta2-HSiFPh2)] 2, whose structure and bonding characteristics have recently been determined by charge density studies based on high-resolution X-ray and neutron diffraction data. The geometry at the Si atom in these sigma-bond complexes is compared with that in other systems containing hypercoordinate silicon. The Mn-H distances for 1 and 2 in solution have been estimated using NMR T1 relaxation measurements, giving a value of 1.56(3) AA in each case, in excellent agreement with the distances deduced from neutron diffraction. DFT calculations have been employed to explore the bonding in the Mn-H-Si unit in 1 and 2 and in the related system [Cp'Mn(CO)2(eta2-HSiCl3)] 3. These studies support the idea that the oxidative addition of a silane ligand to a transition metal center may be described as an asymmetric process in which the Mn-H bond is formed at an early stage, while both the establishment of the Mn-Si bond and also the activation of the eta2-coordinated Si-H moiety are controlled by the extent of Mn-> sigma*(X-Si-H) back-donation, which increases with increasing electronwithdrawing character of the X substituent trans to the metal-coordinated Si-H bond. This delocalized molecular orbital (MO) approach is complemented and supported by combined experimental and theoretical charge density studies including the source function S(r,Omega).
Single-electron Fluorine Bonding. I. The SEFB-15 and CSFB-14 Benchmark Datasets, Reference Binding Energies and Intermolecular Bond Distances: Assessment of M06-2X density functional
Inorganic and Physical Chemistry, Indian Institute of Science（印度科学研究所无机与物理化学）
Organic-Inorganic Hybrid CH3NH3PbI3 Perovskite Solar Cell Nanoclusters: Revealing Ultra-Strong Hydrogen Bonding and Mulliken Inner Complexes and Their Implication in Materials Design
甲基铵碘化铅（CH 3 NH3 PbI 3）钙钛矿太阳能电池由于其作为光捕获半导体的出色器件基础性能而在太阳能电池技术的光伏历史上产生了显著的突破。虽然在过去的4年里，在固态下对该系统的实验和理论研究已经有了大量的报道，但其基本的团簇物理还有待开发。为此，本研究进行了理论研究，使用DFT-M06-2X/ADZP检查的主要几何，电子，拓扑和轨道性质的CH 3 NH3 PbI 3纳米团簇块。这些集群被发现是异常强烈的约束，与位于93.53和125.11千卡mol-1之间的结合能（超过共价极限，40千卡mol-1），使我们能够表征为超强型的潜在的相互作用。基于此，连同异常高的电荷转移，强烈的超共轭相互作用，复杂的拓扑结构的电荷密度，和短的分子间距离发现，我们已经确定了CH 3 NH3 PbI 3作为Mulliken内配合物。此外，这些后果，以及超强相互作用，在设计新的功能纳米材料进行了简要讨论。在这项研究中获得的各种新的结果并不完全符合那些已经报道的实验（Nat. Commun. 2015，6，7124）和计算上（Chem.Commun.，2015，51，6434; Sci. Rep. 2016，doi：10.1038/srep21687; Chem. Mater. 2016，28，4259; J. Mat. Chem A 2016，4，4728; J. Phys. Chem. Lett…
Manifold Diffusion for Structure Generation of Transition Metal Complexes
Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich（苏黎世联邦理工学院化学与生物工程研究所，化学与应用生物科学系）；NCCR Catalysis, Switzerland（瑞士催化中心）
How Molecular Chiralities of Bis(mandelato)borate Anions affect Their Binding Structures with Alkali Metal Ions and Microstructural Properties in Tetraalkylphosphonium Ionic Liquids
