Density Functional Theory Investigations of the Homoleptic Tris(dithiolene) Complexes [M(dddt)3]−q(q= 3, 2 ; M = Nd3+and U3+/4+) Related to Lanthanide(III)/Actinide(III) Differentiation

Meskaldji, Samir; Belkhiri, Lotfi; Arliguie, Thérèse; Fourmigué, Marc; Ephritikhine, Michel; Boucekkine, Abdou

doi:10.1021/ic902135t

Cited by 34 publications

(18 citation statements)

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“…Our previous work [105][106][107][108][109] and several recent studies [68,69,[116][117][118][119][120] have shown that ZORA/BP86/TZP computations reproduce experimental geometries and ground state properties of f-element compounds with a satisfying accuracy.…”

Section: Description Of the Model And Computational Detailsmentioning

confidence: 80%

“…Spin-orbit corrections to the energy difference between the high spin (HS) and BS states have not been considered. These corrections are of atomic nature [105][106][107][108][109][110][111][112], that is, not very sensitive to the environment of the metal ion for a given oxidation state. In the present study, the metal electron configuration is 5f 2 for each U(IV) ion, whatever the HS or BS state, so that neglecting spinorbit corrections seems to be a valid assumption.…”

Section: Description Of the Model And Computational Detailsmentioning

confidence: 99%

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A relativistic DFT study of magnetic exchange coupling in ketimide bimetallic uranium(IV) complexes

et al. 2012

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International audienceMagnetic exchange couplings in bis(ketimide) binuclear UIV/UIV complexes [Cp′2UCl]2(μ-ketimide) diuranium(IV) and [(C5H5)2(Cl)An]2(μ-ketimide) (Cp′ = C5Me4Et; ketimide = N=CMe-(C6H4)-MeC=N) have been investigated computationally using relativistic density functional theory (DFT) combined with the broken symmetry (BS) approach. Using the B3LYP hybrid functional, the BS ground state of these UIV/UIV 5f 2-5f 2 complexes has been found of lower energy than the high spin (HS) quintet state, indicating an antiferromagnetic character (estimated coupling constant |J| < 5 cm−1) which has not yet been evidenced unambiguously experimentally. On the contrary, the BP86 GGA functional overestimates greatly the antiferromagnetic character of the complexes (|J| > 100 cm−1). As recently reported for para-bis(imido) [(C5H5)3U]2(μ-imido) uranium(V) complex, spin polarization is mainly responsible for the antiferromagnetic coupling through the π-network orbital pathway within the bis(ketimide) bridge. Furthermore, spin polarization is exalted by the combined roles of the 5f metal orbitals and of the π-conjugated ketimide bridging ligand which permit electronic communication between the two uranium atoms albeit separated by a distance of the order of 10 Å. The MO analysis clarifies which MOs contribute to the antiferromagnetic coupling in the binuclear complexes under consideration and brings to light the 5f orbitals driving contribution

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Section: Description Of the Model And Computational Detailsmentioning

confidence: 80%

Section: Description Of the Model And Computational Detailsmentioning

confidence: 99%

A relativistic DFT study of magnetic exchange coupling in ketimide bimetallic uranium(IV) complexes

et al. 2012

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“…60 The rapid and reversible electron transfer between the U III and U IV while the ionic radius of uranium(III) is ∼0.02 Å larger than that of cerium(III). Such deviations of U-X distances (X = C, N, I, P, S) from a purely ionic bonding model, which have been observed in a variety of analogous uranium(III) and lanthanide (III) complexes, 61,62 are explained by a stronger, more covalent actinide-ligand interaction. In these anionic and monomeric complexes, the shortening of the U-C(CN) bond length with respect to the corresponding Ce-C(CN) could be an indication of a stronger σ-donation of the ligand towards uranium rather than π back-bonding, as supported by the ν(CN) frequencies.…”

Section: Linear Metallocenes Bent Actinocenes and Half Sandwichesmentioning

confidence: 87%

Advances in f-element cyanide chemistry

2015

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This Dalton perspective gives an overview of the development of cyanide chemistry of 4f- and 5f-elements, a field which was poorly explored in contrast to the attention paid to the cyanide complexes of the d transition metals. The use of the cyanide ligand led to the discovery of mono- and polycyanide complexes which exhibit unprecedented and unexpected coordination geometries. A new type of linear metallocenes including [U(Cp*)2(CN)5](3-) (Cp* = C5Me5) and the first bent actinocenes [An(Cot)2(CN)](-) (An = Th, U; Cot = C8H8) were isolated. Thorocene was found to be much more reactive than uranocene since a series of sterically crowded cyanide complexes have been obtained only from [Th(Cot)2]. A series of cyanido-bridged dinuclear compounds and mononuclear mono-, bis- and tris(cyanide) complexes were prepared by addition of cyanide salts to [MN*3] (M = Ce, U) and [UN*3](+) [N* = N(SiMe3)2]. The Ce(III), U(III) and U(IV) ions were clearly differentiated in these reactions by cyanide linkage isomerism, as shown for example by the structures of the cyanide complex [U(III)N*3(CN)2](2-) and of the isocyanide derivatives [Ce(III)N*3(NC)2](2-) and [U(IV)N*3(NC)](-). While the U-CN/NC coordination preference towards the U(III)/U(IV) pair is related to the subtle balance between steric, covalent and ionic factors, DFT computations and in particular the calculated total bonding energies between the metal and the cyanide ligand allowed the observed coordination mode to be predicted. The ability of the cyanide ligand to stabilize the high oxidation states was assessed with the synthesis of U(V) and U(VI) complexes in the inorganic and organometallic series.

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“…These works revealed that the 5f orbitals in actinide complexes play a significant role in bonding, while the participation of 4f orbitals of lanthanides in bonding appears to be minimal or even negligible [135]. For instance, it was shown that the frontier MOs with important 4f metallic character in Nd III tris(dithiolene) complexes possess zero contribution from the ligands, while in the U(III) system these orbitals are delocalized over the metal and the ligands and contain a substantial 5f contribution [136]. As a result, large-core RECPs, which often provide good results for Ln III complexes, are of more limited application in the case of their actinide counterparts [137].…”

Section: The Nature Of Chemical Bonding In Ln III Complexesmentioning

confidence: 99%

Applications of Density Functional Theory (DFT) to Investigate the Structural, Spectroscopic and Magnetic Properties of Lanthanide(III) Complexes

Platas‐Iglesias¹,

Roca-Sabio²,

Regueiro‐Figueroa³

et al. 2011

CIC

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Density functional theory (DFT) has become a general tool to investigate the structure and properties of complicated inorganic molecules, such as lanthanide(III) coordination compounds, due to the high accuracy that can be achieved at relatively low computational cost. Herein, we present an overview of different successful applications of DFT to investigate the structure, dynamics, vibrational spectra, NMR chemical shifts, hyperfine interactions, excited states, and magnetic properties of lanthanide(III) complexes. We devote particular attention to our own work on the conformational analysis of LnIII-polyaminocarboxylate complexes. Besides, a short discussion on the different approaches used to investigate lanthanide(III) complexes, i. e. all-electron relativistic calculations and the use of relativistic effective core potentials (RECPs), is also presented. The issue of whether the 4f electrons of the lanthanides are involved in chemical bonding or not is also shortly discussed.

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Density Functional Theory Investigations of the Homoleptic Tris(dithiolene) Complexes [M(dddt)₃]^−q(q= 3, 2 ; M = Nd³⁺and U^3+/4+) Related to Lanthanide(III)/Actinide(III) Differentiation

Cited by 34 publications

References 35 publications

A relativistic DFT study of magnetic exchange coupling in ketimide bimetallic uranium(IV) complexes

A relativistic DFT study of magnetic exchange coupling in ketimide bimetallic uranium(IV) complexes

Advances in f-element cyanide chemistry

Applications of Density Functional Theory (DFT) to Investigate the Structural, Spectroscopic and Magnetic Properties of Lanthanide(III) Complexes

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