Similar ligand–metal bonding for transition metals and actinides? 5f 1 U(C 7 H 7 ) 2 − versus 3d n metallocenes
Abstract
U(C7H7)2- is an intriguing 5f1 complex whose metal–ligand bonding was assigned in the literature as being very similar to 3d7 cobaltocene, based on a crystal-field theoretical interpretation of the experimental magnetic resonance data. The present work provides an in-depth theoretical study of the electronic structure, bonding, and magnetic properties of the 5f1 U(C7H7)2-vs. 3d metallocenes with V, Co, and Ni, performed with relativistic wavefunction and density functional methods. The ligand to metal donation bonding in U(C7H7)2- is strong and in fact similar to that in vanadocene, in the sense that the highest occupied arene orbitals donate electron density into empty metal orbitals of the same symmetry with respect to the rotational axis (3dπ for V, 5fδ for U), but selectively with α spin (↑). For Co and Ni, the dative bonding from the ligands is β spin (↓) selective into partially filled 3dπ orbitals. In all systems, this spin delocalization triggers spin polarization in the arene σ bonding framework, causing proton spin densities opposite to those of the carbons. Because of this, the proton spin densities and hyperfine coupling constants A$$1h\atop{iso}$$ are negative for the Co and Ni complex, but positive for vanadocene. The A$$1h\atop{iso}$$ of U(C7H7)2- is negative and similar to that of cobaltocene, but only because of the strong spin–orbit coupling in the actinocene, which causes A$$1h\atop{iso}$$ to be opposite to the sign of the proton spin density. The study contributes to a better understanding of actinide 5f vs. transition metal 3d covalency, and highlights potential pitfalls when interpreting experimental magnetic resonance data in terms of covalent bonding for actinide complexes.
- Authors:
-
[1];
[1];
[1]
- Department of Chemistry, University at Buffalo, State University of New York, Buffalo, USA
- Publication Date:
- Research Org.:
- Univ. of Maryland, College Park, MD (United States); Research Foundation (RF) for the State Univ. of New York (SUNY), Amherst, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1459033
- Alternate Identifier(s):
- OSTI ID: 1505227
- Grant/Contract Number:
- SC0001136; SC0001160
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 29; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Sergentu, Dumitru-Claudiu, Gendron, Frédéric, and Autschbach, Jochen. Similar ligand–metal bonding for transition metals and actinides? 5f 1 U(C 7 H 7 ) 2 − versus 3d n metallocenes. United Kingdom: N. p., 2018.
Web. doi:10.1039/C7SC05373H.
Sergentu, Dumitru-Claudiu, Gendron, Frédéric, & Autschbach, Jochen. Similar ligand–metal bonding for transition metals and actinides? 5f 1 U(C 7 H 7 ) 2 − versus 3d n metallocenes. United Kingdom. https://doi.org/10.1039/C7SC05373H
Sergentu, Dumitru-Claudiu, Gendron, Frédéric, and Autschbach, Jochen. Mon .
"Similar ligand–metal bonding for transition metals and actinides? 5f 1 U(C 7 H 7 ) 2 − versus 3d n metallocenes". United Kingdom. https://doi.org/10.1039/C7SC05373H.
@article{osti_1459033,
title = {Similar ligand–metal bonding for transition metals and actinides? 5f 1 U(C 7 H 7 ) 2 − versus 3d n metallocenes},
author = {Sergentu, Dumitru-Claudiu and Gendron, Frédéric and Autschbach, Jochen},
abstractNote = {U(C7H7)2- is an intriguing 5f1 complex whose metal–ligand bonding was assigned in the literature as being very similar to 3d7 cobaltocene, based on a crystal-field theoretical interpretation of the experimental magnetic resonance data. The present work provides an in-depth theoretical study of the electronic structure, bonding, and magnetic properties of the 5f1 U(C7H7)2-vs. 3d metallocenes with V, Co, and Ni, performed with relativistic wavefunction and density functional methods. The ligand to metal donation bonding in U(C7H7)2- is strong and in fact similar to that in vanadocene, in the sense that the highest occupied arene orbitals donate electron density into empty metal orbitals of the same symmetry with respect to the rotational axis (3dπ for V, 5fδ for U), but selectively with α spin (↑). For Co and Ni, the dative bonding from the ligands is β spin (↓) selective into partially filled 3dπ orbitals. In all systems, this spin delocalization triggers spin polarization in the arene σ bonding framework, causing proton spin densities opposite to those of the carbons. Because of this, the proton spin densities and hyperfine coupling constants A$1h\atop{iso}$ are negative for the Co and Ni complex, but positive for vanadocene. The A$1h\atop{iso}$ of U(C7H7)2- is negative and similar to that of cobaltocene, but only because of the strong spin–orbit coupling in the actinocene, which causes A$1h\atop{iso}$ to be opposite to the sign of the proton spin density. The study contributes to a better understanding of actinide 5f vs. transition metal 3d covalency, and highlights potential pitfalls when interpreting experimental magnetic resonance data in terms of covalent bonding for actinide complexes.},
doi = {10.1039/C7SC05373H},
journal = {Chemical Science},
number = 29,
volume = 9,
place = {United Kingdom},
year = {Mon Jan 01 00:00:00 EST 2018},
month = {Mon Jan 01 00:00:00 EST 2018}
}
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Works referencing / citing this record:
Uranocenium: Synthesis, Structure, and Chemical Bonding
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Prediction of high bond-order metal–metal multiple-bonds in heterobimetallic 3d–4f/5f complexes [TM–M{N( o -[NCH 2 P(CH 3 ) 2 ]C 6 H 4 ) 3 }] (TM = Cr, Mn, Fe; M = U, Np, Pu, and Nd)
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