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 com...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.展开更多
基金supported by the National Natural Science Foundation of China(No.21873020 and No.21688102)。
文摘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.
