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Infrared Spectra,Structures and bonding of Binuclear Transition metal Carbonyl Cluster Ions

Chinese Journal of Chemical Physics 2018年第1期31卷 1-11,I0001页

作者：王冠军周鸣飞复旦大学化学系能源材料化学协同创新中心上海市分子催化和功能材料重点实验室

Binuclear transition metal carbonyl clusters serve as the simplest models in understand- ing metal-metal and ligand bonding that are important organometallic chemistry catalysis. Binuclear first row transition metal carbonyl ions are produced via a pulsed laser vaporiza- tion/supersonic expansion cluster ion source in the gas phase. These ions are studied by mass-selected infrared photodissociation spectroscopy in the carbonyl stretching frequency region. Density functional theory calculations have been performed on the geometric struc- tures and vibrational spectra of the carbonyl ions. Their geometric and electronic structures are determined by comparison of the experimental IR spectra with the simulated spectra. The structure and the metM-metal and metal-CO bonding of both saturated and unsaturated homonuclear as well as heteronuclear carbonyl cluster cations and anions are discussed.

关键词： Transition metal carbonyl complex Infrared photodissociation spectroscopy metal-metal bonding metal-ligand interaction The 18-electron rule

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Lu2C2n(2n=76-90): Crystallographic Steering the Configuration of the Internal Cluster by Altering the Outer Cage Size

Lu2C2n(2n=76-90): Crystallographic Steering the Configuratio...

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中国化学会第十届全国无机化学学术会议

作者： Wangqiang Shen Xing Lu State Key Laboratory of Materials Processing and Die & Mould Technology School of Materials Science and EngineeringHuazhong University of Science and Technology

Fullerenes as the only molecular form of carbon allotrope with accurate structures,canaccommodate a variety of metal elements to form endohedral metallofullerenes (EMFs),providing an ideal platform for the study of metal-carbon interactions at the atomic ***,we reveal for the first time the decisive effect of the cage size on steering the configuration of the encapsulated cluster based on our concrete X-ray results of fourteen lutetium-containing endohedrals,Lu2C2n (2n=76-90).The results reveal that the small cages (2n=76-88) can only accommodate a Lu cluster because of the limited inner space,accompanied by the possible formation of a Lu–Lu ***,when the cage expands further (2n=86-92),a C2-unit is inserted between the two Lu atoms,which takes over partially the charges from the metals and coordinates with them,making the whole system more ***,we confirm for the first time that the preferential formation of the Lu2@C2n/Lu2C2@C2n–2 composition is determined by the outer cage size,presenting a practical strategy for the templated synthesis of EMFs possessing desired internal clusters,which may facilitate the application of EMFs as building blocks for molecular devices/machines.

关键词： Endohedral metallofullerenes X-ray diffraction crystallography Cage size effect metal-metal bonding Carbide cluster

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Transition metal Induced β-H Elimination of Magnesium alkyls

Transition Metal Induced β-H Elimination of Magnesium alkyl...

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中国化学会第十届全国无机化学学术会议

作者：黄佳苏徐信 Key Laboratory of Organic Synthesis of Jiangsu Province College of chemistry Chemical Engineering and Materials Science Soochow University

The preparation and application of multimetallic complexes containing direct metal-metal bonds continue to occupy researchers in the fields of organometallic, main group, and coordination chemistry. Since the 1970 s, there have been occasional reports of structurally authenticated compounds with alkaline earth metal-transition metal bonds. Herein, we found that transition metal were able to induce β-H elimination of magnesium alkyl complexes to produce heterotrimetallic hydride-bridged Mg-Ni-Mg complexes with short Mg-Ni bonds. In addition, a heterobimetallic hydride-bridged Mg-Ni intermediate was also isolated and characterized. The structural data suggested that 1 and 2 possibly behaved as stretched σ-Mg-H complexes. Herein, we will present these results.

关键词： magnesium β-H elimination σ-complex metal-metal bonding

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