Large relativistic effects in 119Sn NMR parameters: A case study of complex anions [Cp*M(SnCl3)nCl3−n]−, where M = Rh, Ir; n = 1, 2, 3

Mirzaeva, Irina V.

doi:10.1016/j.comptc.2021.113432

Cited by 5 publications

(2 citation statements)

References 65 publications

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“…The properties of bond critical points are shown in Table S4. Re–Re and all the Re–ligand bonds are of the intermediate type (neither closed-shell, nor shared), which is common for the bonds involving transition metals . Higher electron density values, compared to such values for single Re–Re bonds, confirm that Re–Re bonds are double, just as initially proposed .…”

Section: Resultssupporting

confidence: 55%

The Cluster Polyazide Complexes: Synthesis, Crystal Structures, and¹⁴N NMR Studies of [{Re₃(μ-X)₃}(N₃)₉]^3–(X = Br or I)

et al. 2022

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Azide cluster complexes [{Re3(μ-Br)3}(N3)9]3– and [{Re3(μ-I)3}(N3)9]3– were obtained by reaction of Re3X9 (X = Br or I, respectively) with sodium azide in methanol. The complexes were crystallized as cesium salts of the compositions Cs3[{Re3(μ-Br)3}(N3)9]·H2O (1) and Cs3[{Re3(μ-I)3}(N3)9]·H2O (2) and characterized by X-ray single-crystal diffraction and elemental analyses, mass spectrometry, 14N NMR spectroscopy, and DFT calculations. In the anions, each rhenium atom is coordinated by three azide ligands. To the best of our knowledge, these compounds represent the first case of metal cluster polyazide complexes (i.e., where each metal atom bears more than one azide ligand). Both complexes are stable in air but are very shock sensitive, and spontaneous explosive decomposition is also possible.

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Section: Resultssupporting

confidence: 55%

The Cluster Polyazide Complexes: Synthesis, Crystal Structures, and¹⁴N NMR Studies of [{Re₃(μ-X)₃}(N₃)₉]^3–(X = Br or I)

et al. 2022

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“…Recent years have seen many applications of LMO analyses of calculated NMR parameters such as shielding or the Jcoupling tensor elements for heavy elements across the periodic table . Examples include studies of heavy-atom (HA) effects on NMR tensors, [14][15][16][17] shielding and J-coupling tensors of main group and transition metals, [18][19][20][21][22][23][24][25][26][27] or the nature of chemical bonding with actinides as probed by NMR measurements. [15,28,29] Therefore, we thought it timely and relevant to provide a brief account of the analysis methodology, along with an example.…”

Section: Introductionmentioning

confidence: 99%

Relativistic Density Functional NMR Tensors Analyzed with Spin‐free Localized Molecular Orbitals

Fernández‐Alarcón

Autschbach

2022

ChemPhysChem

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The implementation of fast relativistic methods based on density functional theory, in conjunction with localized molecular orbital (LMO) based analysis, allows straightforward interpretations of NMR parameters in terms of contributions from core shells, lone pairs, and bonds, for compounds containing elements from across the periodic table. We present a conceptual review of a frequently used LMO analysis of NMR parameters calculated in the presence of spin‐orbit interactions and other relativistic effects. An accompanying example focuses on the 15N shielding in a heavy metal complex.

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Dynamic and relativistic effects on Pt–Pt indirect spin–spin coupling in aqueous solution studied by ab initio molecular dynamics and two- vs four-component density functional NMR calculations

Batista,

Ducati,

Autschbach

2024

The Journal of Chemical Physics

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Treating 195Pt nuclear magnetic resonance parameters in solution remains a considerable challenge from a quantum chemistry point of view, requiring a high level of theory that simultaneously takes into account the relativistic effects, the dynamic treatment of the solvent–solute system, and the dynamic electron correlation. A combination of Car-Parrinello molecular dynamics (CPMD) and relativistic calculations based on two-component zeroth order regular approximation spin–orbit Kohn–Sham (2c-ZKS) and four-component Dirac–Kohn–Sham (4c-DKS) Hamiltonians is performed to address the solvent effect (water) on the conformational changes and JPtPt1 coupling. A series of bridged PtIII dinuclear complexes [L1–Pt2(NH3)4(Am)2–L2]n+ (Am = α–pyrrolidonate and pivalamidate; L = H2O, Cl−, and Br−) are studied. The computed Pt–Pt coupling is strongly dependent on the conformational dynamics of the complexes, which, in turn, is correlated with the trans influence among axial ligands and with the angle N–C–O from the bridging ligands. The J-coupling is decomposed in terms of dynamic contributions. The decomposition reveals that the vibrational and explicit solvation contributions reduce JPtPt1 of diaquo complexes (L1 = L2 = H2O) in comparison to the static gas-phase magnitude, whereas the implicit solvation and bulk contributions correspond to an increase in JPtPt1 in dihalo (L1 = L2 = X−) and aquahalo (L1 = H2O; L2 = X−) complexes. Relativistic treatment combined with CPMD shows that the 2c-ZKS Hamiltonian performs as well as 4c-DKS for the JPtPt1 coupling.

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Large relativistic effects in 119Sn NMR parameters: A case study of complex anions [Cp*M(SnCl3)nCl3−n]−, where M = Rh, Ir; n = 1, 2, 3

Cited by 5 publications

References 65 publications

The Cluster Polyazide Complexes: Synthesis, Crystal Structures, and¹⁴N NMR Studies of [{Re₃(μ-X)₃}(N₃)₉]^3–(X = Br or I)

The Cluster Polyazide Complexes: Synthesis, Crystal Structures, and¹⁴N NMR Studies of [{Re₃(μ-X)₃}(N₃)₉]^3–(X = Br or I)

Relativistic Density Functional NMR Tensors Analyzed with Spin‐free Localized Molecular Orbitals

Dynamic and relativistic effects on Pt–Pt indirect spin–spin coupling in aqueous solution studied by ab initio molecular dynamics and two- vs four-component density functional NMR calculations

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Large relativistic effects in 119Sn NMR parameters: A case study of complex anions [Cp*M(SnCl3)nCl3−n]−, where M = Rh, Ir; n = 1, 2, 3

Cited by 5 publications

References 65 publications

The Cluster Polyazide Complexes: Synthesis, Crystal Structures, and14N NMR Studies of [{Re3(μ-X)3}(N3)9]3–(X = Br or I)

The Cluster Polyazide Complexes: Synthesis, Crystal Structures, and14N NMR Studies of [{Re3(μ-X)3}(N3)9]3–(X = Br or I)

Relativistic Density Functional NMR Tensors Analyzed with Spin‐free Localized Molecular Orbitals

Dynamic and relativistic effects on Pt–Pt indirect spin–spin coupling in aqueous solution studied by ab initio molecular dynamics and two- vs four-component density functional NMR calculations

Contact Info

Product

Resources

About

The Cluster Polyazide Complexes: Synthesis, Crystal Structures, and¹⁴N NMR Studies of [{Re₃(μ-X)₃}(N₃)₉]^3–(X = Br or I)

The Cluster Polyazide Complexes: Synthesis, Crystal Structures, and¹⁴N NMR Studies of [{Re₃(μ-X)₃}(N₃)₉]^3–(X = Br or I)