Electronic Structure,Excited States,and Photoelectron Spectra of Uranium,Thorium,and Zirconium Bis(Ketimido)Complexes(C_5R_5)_2M-NCPH_2_2(M = Th,U,Zr;R = H,CH_3)

Aurora E.Clark; Richard L.Martin; P.Jeffrey HayJennifer C.GreenKimberly C.JantunenJaqueline L.Kiplinger

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Electronic Structure,Excited States,and Photoelectron Spectra of Uranium,Thorium,and Zirconium Bis(Ketimido)Complexes(C_5R_5)_2M-NCPH_2_2(M = Th,U,Zr;R = H,CH_3)

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Organometallic actinide bis(ketimide)complexes(C_5Me_5)_2An-N=C(Ph)(R)_2(where R = Ph,Me,and CH_~2Ph)of thorium(IV)and uranium(IV)have recently been synthesized that exhibit chemical,structural,and spectroscopic(UV-Visible,resonance-enhanced Raman)evidence for unusual actinide-ligand bonding.Da Re et al.,/.Am.Chem.Soc.,2005,727,682;Jantunen et al.,Organometallics,2004,23,4682;Morris et al.,Organometallics,2004,23,5142. Similar evidence has been observed for the group 4 analogue(C_5H_5)_2-Zr-N=CPH_2_2.Da Re et al.,J.Am.Chem.Soc.,2005,727,682. These compounds have important implications for the development of new heavy-element systems that possess novel electronic and magnetic properties.Here,we have investigated M-ketimido bonding(M = Th,U,Zr),as well as the spectroscopic properties of the highly colored bis-ketimido complexes,using density functional theory(DFT).Photoelectron spectroscopy(PES)has been used to experimentally elucidate the ground-state electronic structure of the thorium and uranium systems.Careful examination of the ground-state electronic structure,as well as a detailed modeling of the photoelectron spectra,reveals similar bonding interactions between the thorium and uranium compounds.Using time-dependent DFT(TDDFT),we have assigned the bands in the previously reported UV-Visible spectra for(C_5Me_5)_2Th-N=CPH_2_2,(C_5Me_5)_2U-N=CPH_2_2,and(C_5H_5)_2Zr-N=CPH_2_2.The low-energy transitions are attributed to ligand-localized N p-> C=N pi* excitations.These excited states may be either localized on a single ketimido unit or may be of the ligand-ligand charge-transfer type.Higher-energy transitions are cyclopentadienyl pi-> CN pi* or cyclopentadienyl pi - phenyl pi* in character.The lowest-energy excitation in the(C_5Me_5)_2U-N=PH_2_2 compound is attributed to f-f and metal-ligand charge-transfer transitions that are not available in the thorium and zirconium analogues.Geometry optimization and vibrational analysis of the lowest-energy triplet state of the zirconium and thorium compounds also aids in the assignment and understanding of the resonance-enhanced Raman data that has recently been reported.Da Re et al.,J.Am.Chem.Soc.,2005,727,682.

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2005年第24期|5481-5491|共11页
作者
Aurora E.Clark; Richard L.Martin; P.Jeffrey HayJennifer C.GreenKimberly C.JantunenJaqueline L.Kiplinger;
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Theoretical Division,Los Alamos National Laboratory,Mail Stop B268,Los Alamos,New Mexico 87545;

Inorganic Chemistry Laboratory,University of Oxford,South Parks Road,Oxford,OX1 3QR,United Kingdom;

Chemistry Division,Los Alamos National Laboratory,Mail Stop J514,Los Alamos,New Mexico 87545;

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中图分类物理化学（理论化学）、化学物理学;
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Electronic Structure,Excited States,and Photoelectron Spectra of Uranium,Thorium,and Zirconium Bis(Ketimido)Complexes(C_5R_5)_2M-NCPH_2_2(M = Th,U,Zr;R = H,CH_3)

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