Mononuclear Carbonyl Anion Complexes of GroupsⅣandⅤMetals  

钛族和钒族金属的单核金属羰基负离子配合物

作　　者：Shu-jun Lei Yang-yu Zhou Xiao-yang Jin Guan-jun Wang Ming-fei Zhou 雷书俊;周洋宇;金晓阳;王冠军;周鸣飞(复旦大学化学系,上海市分子催化与功能材料重点实验室,能源材料化学协同中心,上海200438)

机构地区：[1]Collaborative Innovation Center of Chemistry for Energy Materials,Department of Chemistry,Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials,Fudan University,Shanghai 200438,China

出　　处：《Chinese Journal of Chemical Physics》2022年第6期867-874,I0005-I0010,I0072,共15页化学物理学报（英文）

基　　金：supported by the National Natural Science Foundation of China(No.21873020 and No.21688102)。

摘　　要：The anionic carbonyl complexes of groupsⅣandⅤmetals TM(CO)6,7(TM=Ti,Zr,Hf,V,Nb,Ta)are prepared in the gas phase using a laser vaporation-supersonic expansion ion source.The infrared spectra of TM(CO)_(6,7)-anion complexes in the carbonyl stretching frequency region are measured by mass-selected infrared photodissociation spectroscopy.The six-coordinated TM(CO)_(6)-anions are determined to be the coordination saturate complexes for both the groupⅣand groupⅤmetals.The TM(CO)_(6)-complexes of groupⅣmetals(TM=Ti,Zr,Hf)are 17-electron complexes having a~2A1gground state with D3dsymmetry,while the TM(CO)_(6)-complexes of groupⅤmetals(TM=Ⅴ,Nb,Ta)are 18-electron species with a closed-shell singlet ground state possessing Ohsymmetry.The energy decomposition analyses indicate that the metal-CO covalent bonding is dominated by TM-(d)→(CO)6π-backdonation and TM-(d)←(CO)6σ-donation interactions.

关 键 词：Infrared photodissociation spectroscopy Metal carbonyl complex 18-Electron rule Molecular structure 

分 类 号：O641.4[理学—物理化学]