The anionic carbonyl complexes of groups Ⅳ and Ⅴ metals 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 car-bonyl stretching frequency region are measured by mass-selected infrared pho-todissociation spectroscopy.The six-coordinated TM(CO)6-anions are determined to be the coordination saturate complexes for both the group Ⅳ and group Ⅴ metals.The TM(CO)6-complexes of group Ⅳ metals(TM=Ti,Zr,Hf)are 17-electron complexes having a 2Aig ground state with D3d symmetry,while the TM(CO)6-complexes of group Ⅴ metals(TM=V,Nb,Ta)are 18-electron species with a closed-shell singlet ground state possessing Oh symmetry.The energy decomposition analyses indicate that the metal-CO covalent bonding is dominated by TM-(d)→(CO)6π-backdonation and TM-(d)←(CO)6 σ-donation interactions.

Shu-jun Lei;Yang-yu Zhou;Xiao-yang Jin;Guan-jun Wang;Ming-fei Zhou

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

化学物理学报（英文版）

[1]Shu-jun Lei;Yang-yu Zhou;Xiao-yang Jin;Guan-jun Wang;Ming-fei Zhou-.Mononuclear Carbonyl Anion Complexes of Groups Ⅳ and Ⅴ Metals)[J].化学物理学报（英文版）,2022(06):867-874

vaporation,bonyl,todissociation,2Aig,backdonation

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