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Title: The roles of 4f- and 5f-orbitals in bonding: A magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study

Journal Article · · Dalton Transactions
DOI: https://doi.org/10.1039/C6DT00634E · OSTI ID:1341858
 [1];  [2]; ORCiD logo [3];  [4];  [4];  [5]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. RWTH Aachen Univ., Aachen (Germany)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Univ. at Buffalo, State Univ. of New York, Buffalo, NY (United States)
  5. RWTH Aachen Univ., Aachen (Germany); Forschungszentrum Julich, Julich (Germany)
+ Show Author Affiliations

The electronic structures of 4f3/5f3 Cp"3M and Cp"3M·alkylisocyanide complexes, where Cp" is 1,3-bis-(trimethylsilyl)cyclopentadienyl, are explored with a focus on the splitting of the f-orbitals, which provides information about the strengths of the metal–ligand interactions. While the f-orbital splitting in many lanthanide complexes has been reported in detail, experimental determination of the f-orbital splitting in actinide complexes remains rare in systems other than halide and oxide compounds, since the experimental approach, crystal field analysis, is generally significantly more difficult for actinide complexes than for lanthanide complexes. In this study, a set of analogous neodymium(III) and uranium(III) tris-cyclopentadienyl complexes and their isocyanide adducts was characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility. The crystal field model was parameterized by combined fitting of EPR and susceptibility data, yielding an accurate description of f-orbital splitting. The isocyanide derivatives were also studied using density functional theory, resulting in f-orbital splitting that is consistent with crystal field fitting, and by multi-reference wavefunction calculations that support the electronic structure analysis derived from the crystal-field calculations. The results highlight that the 5f-orbitals, but not the 4f-orbitals, are significantly involved in bonding to the isocyanide ligands. The main interaction between isocyanide ligand and the metal center is a σ-bond, with additional 5f to π* donation for the uranium complexes. As a result, while interaction with the isocyanide π*-orbitals lowers the energies of the 5fxz2 and 5fyz2-orbitals, spin–orbit coupling greatly reduces the population of 5fxz2 and 5fyz2 in the ground state.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC52-06NA25396; AC02-05CH11231
OSTI ID:
1341858
Alternate ID(s):
OSTI ID: 1435061
Report Number(s):
LA-UR-15-29482; ICHBD9
Journal Information:
Dalton Transactions, Vol. 45, Issue 28; ISSN 1477-9226
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 43 works
Citation information provided by
Web of Science

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Cited By (8)

[Am(C 5 Me 4 H) 3 ]: An Organometallic Americium Complex journal July 2019
Spectroscopic Determination of the Electronic Structure of a Uranium Single-Ion Magnet journal January 2019
CONDON 3.0: An Updated Software Package for Magnetochemical Analysis-All the Way to Polynuclear Actinide Complexes: CONDON 3.0: An Updated Software Package for Magnetochemical Analysis: All the Way to Polynuclear Actinide Complexes journal September 2018
Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy journal December 2016
Bis(nitrilo)tris(methylenephosphonato)dodecaaquatrihydrohexasodium Europium(III) [EuNa6H3(H2O)12{N(CH2PO3)3}2]: Synthesis and Structure journal May 2018
Decomposition of d- and f-Shell Contributions to Uranium Bonding from the Quantum Theory of Atoms in Molecules: Application to Uranium and Uranyl Halides journal August 2018
DFT Investigations of the Magnetic Properties of Actinide Complexes journal February 2019
[Am(C 5 Me 4 H) 3 ]: An Organometallic Americium Complex journal July 2019

Figures / Tables (16)

Table 1(p. 6)table Table 1
Table 2(p. 6)table Table 2
Fig. 1(p. 7)figure Fig. 1
Fig. 2(p. 7)figure Fig. 2
Table 3(p. 7)table Table 3
Fig. 3(p. 8)figure Fig. 3
Fig. 4(p. 9)figure Fig. 4
Fig. 5(p. 9)figure Fig. 5
Table 4(p. 9)table Table 4
Fig. 6(p. 10)figure Fig. 6
Fig. 7(p. 10)figure Fig. 7
Fig. 8(p. 11)figure Fig. 8
Fig. 9(p. 11)figure Fig. 9
Fig. 10(p. 12)figure Fig. 10
Fig. 11(p. 12)figure Fig. 11
Table 5(p. 13)table Table 5

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