Theoretical Studies on Uranium-Iron Triple-Bonded UFe（CO）₃^- and OUFe（CO）₃^- Complexes

【作者】 王佳琦； 周鸣飞； 李隽；

【Author】 Jiaqi Wang;Mingfei Zhou;Jun Li;Department of Chemistry,Tsinghua University;Department of Chemistry,Fudan University;

【机构】 Department of Chemistry,Tsinghua University； Department of Chemistry,Fudan University；

【摘要】 Understanding of actinide multiple bonding is vital in f-element chemistry. While actinide-containing metal-ligand multiple bonds are known,actinide-transition metal multiple bonds are extremely rare. [1] We report here theoretical studies on the first such species UFe（CO）₃^-and OUFe（CO）₃^-that are prepared in the gas phase and characterized with mass spectrometry,infrared photodissociation spectroscopy and relativistic quantum chemistry. [2]Theoretical calculations were performed with density functional theory（DFT）and wavefunction theory（WFT） at the levels of Hartree-Fock, CCSD（T） and CASPT2. It is shown that both anions have C3 v structures with all the carbonyl ligands coordinated to the iron center. They are found to possess very short U-F bond distances involving one "electron-sharing" σ bond and two Fe-to-U πdative covalent bonds. Our work reveals that there exists a new type of df-d metal-metal multiple bonding, involving dative donation from fully occupied transition metal（n-1）d-orbitals to empty outer-shell 5f6d-orbitals of actinides.更多还原

【Abstract】 Understanding of actinide multiple bonding is vital in f-element chemistry. While actinide-containing metal-ligand multiple bonds are known,actinide-transition metal multiple bonds are extremely rare. [1] We report here theoretical studies on the first such species UFe（CO）₃^-and OUFe（CO）₃^-that are prepared in the gas phase and characterized with mass spectrometry,infrared photodissociation spectroscopy and relativistic quantum chemistry. [2]Theoretical calculations were performed with density functional theory（DFT）and wavefunction theory（WFT） at the levels of Hartree-Fock, CCSD（T） and CASPT2. It is shown that both anions have C3 v structures with all the carbonyl ligands coordinated to the iron center. They are found to possess very short U-F bond distances involving one "electron-sharing" σ bond and two Fe-to-U πdative covalent bonds. Our work reveals that there exists a new type of df-d metal-metal multiple bonding, involving dative donation from fully occupied transition metal（n-1）d-orbitals to empty outer-shell 5f6d-orbitals of actinides.更多还原