Measurement of Δ1J(199Hg, 31P) in [HgPCy3(OAc)2]2 and relativistic ZORA DFT investigations of mercury–phosphorus coupling tensors

Bryce, David L.; Courchesne, Noémie‐Manuelle Dorval; Perras, Frédéric A.

doi:10.1016/j.ssnmr.2009.11.004

Cited by 15 publications

(16 citation statements)

References 60 publications

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“…)/Hz has been used in this work to convert between J and K for spin-spin coupling between 13 C and 199 Hg nuclei.…”

Section: Methodsmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] 199 Hg NMR parameters have been studied for several decades, because this spin 1/2 nucleus does not have a quadrupole moment. Besides being of fundamental physicochemical interest, for instance in the context of measurements of chemical shift and J coupling tensor anisotropies, [11,13,16] Hg NMR spectroscopy also finds applications in the study of biochemically relevant systems. [12,17,18] A particularly interesting aspect of 199 Hg NMR spectroscopy is that mercury chemical shifts, coupling constants (J) involving Hg, as well as the tensor properties of its nuclear magnetic shielding and J coupling, are strongly influenced by relativistic effects.…”

Section: Introductionmentioning

confidence: 99%

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Modeling of Heavy‐Atom–Ligand NMR Spin–Spin Coupling in Solution: Molecular Dynamics Study and Natural Bond Orbital Analysis of HgC Coupling Constants

Zheng

Autschbach

2010

Chemistry A European J

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Ab initio molecular dynamics (MD) and relativistic density functional NMR methods were applied to calculate the one-bond Hg-C NMR indirect nuclear spin-spin coupling constants (J) of [Hg(CN)(2) ] and [CH(3) HgCl] in solution. The MD averages were obtained as J((199) Hg-(13) C)=3200 and 1575 Hz, respectively. The experimental Hg-C spin-spin coupling constants of [Hg(CN)(2) ] in methanol and [CH(3) HgCl] in DMSO are 3143 and 1674 Hz, respectively. To deal with solvent effects in the calculations, finite "droplet" models of the two systems were set up. Solvent effects in both systems lead to a strong increase of the Hg-C coupling constant. From a relativistic natural localized molecular orbital (NLMO) analysis, it was found that the degree of delocalization of the Hg 5d(σ) nonbonding orbital and of the HgC bonding orbital between the two coupled atoms, the nature of the trans Hg-C/Cl bonding orbital, and the s character of these orbitals, exhibit trends upon solvation of the complexes that, when combined, lead to the strong increase of J(Hg-C).

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“…)/Hz has been used in this work to convert between J and K for spin-spin coupling between 13 C and 199 Hg nuclei.…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Modeling of Heavy‐Atom–Ligand NMR Spin–Spin Coupling in Solution: Molecular Dynamics Study and Natural Bond Orbital Analysis of HgC Coupling Constants

Zheng

Autschbach

2010

Chemistry A European J

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“…The Cd-N Im bond lengths ranged from 2.3602(15)-2.4313(15) Å, consistent with strong σ bonding interactions. The 2.9715 (14) Å bond between the central amine and Cd(II) was considerably longer, but within the sum of the van der Waals radii. Complex 1 had slightly shorter M-N Am and average M-N Im bond lengths than [Hg(L1) 2 ](ClO 4 ) 2 (6).…”

Section: Syntheses and Solid State Characterizationsmentioning

confidence: 95%

“…The relativistic contributions to heavy metal coupling constants enable sizable through bond and through space coupling constants. [11][12][13][14][15][16][17] The theory for understanding relativistic interactions is an active area of research. Other established factors in the magnitude of coupling interactions include the internuclear separation 17 and geometric parameters such as torsion angles, 17,18 as well as the efficiency of agostic spin density transfer.…”

Section: Introductionmentioning

confidence: 99%

Bis-tetradentate complexes of Cd(ii) and Hg(ii) with N₈coordination: structural and NMR comparisons

et al. 2014

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Tripodal N4 ligands tris[(1-methylimidazol-2-yl)methyl]amine (L1), bis[(1-methylimidazol-2-yl)methyl][(2-pyridyl)methyl]amine (L2) and [(1-methylimidazol-2-yl)methyl]-bis-[(2-pyridyl)methyl]amine (L3) were used to prepare five new [ML2](ClO4)2 (M = Cd(II), Hg(II)) complexes. All complexes had N8 metal coordination and a trans-bicapped octahedral structure as determined by X-ray crystallography. Metal-nitrogen bond distances generally decreased in the order M-Namine > M-Npyridyl > M-Nimidazoyl, and the perchlorates were well separated from the metal ions. Variable temperature solution state (1)H NMR spectroscopy revealed conditions for slow intramolecular reorganization were more readily accessible for the Cd(II) complexes than for the Hg(II) complexes. Both protons of imidazoyl ring ligand components had large, comparable J((199)Hg(1)H) despite sizable differences in nuclear separation.

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“…However, this symmetry is not enforced (see Ref. 28 for a discussion of the experimental implications of the non‐coincidence of J and D) and further work is required to explore the relation between the orientation of J and D.…”

Section: Experimental Considerationsmentioning

confidence: 99%

Prediction of NMR J-coupling in solids with the planewave pseudopotential approach

Yates¹

2010

Magn. Reson. Chem.

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We review the calculation of NMR J-coupling in solid materials using the planewave pseudopotential formalism of Density Functional Theory. The methodology is briefly summarised and an account of recent applications is given. We discuss various aspects of the calculations which should be taken into account when comparing results with solid-state NMR experiments including anisotropy and orientation of the J tensors, the reduced coupling constant, and the relation between J and crystal structure.

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Measurement of Δ1J(199Hg, 31P) in [HgPCy3(OAc)2]2 and relativistic ZORA DFT investigations of mercury–phosphorus coupling tensors

Cited by 15 publications

References 60 publications

Modeling of Heavy‐Atom–Ligand NMR Spin–Spin Coupling in Solution: Molecular Dynamics Study and Natural Bond Orbital Analysis of HgC Coupling Constants

Modeling of Heavy‐Atom–Ligand NMR Spin–Spin Coupling in Solution: Molecular Dynamics Study and Natural Bond Orbital Analysis of HgC Coupling Constants

Bis-tetradentate complexes of Cd(ii) and Hg(ii) with N₈coordination: structural and NMR comparisons

Prediction of NMR J-coupling in solids with the planewave pseudopotential approach

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Measurement of Δ1J(199Hg, 31P) in [HgPCy3(OAc)2]2 and relativistic ZORA DFT investigations of mercury–phosphorus coupling tensors

Cited by 15 publications

References 60 publications

Modeling of Heavy‐Atom–Ligand NMR Spin–Spin Coupling in Solution: Molecular Dynamics Study and Natural Bond Orbital Analysis of HgC Coupling Constants

Modeling of Heavy‐Atom–Ligand NMR Spin–Spin Coupling in Solution: Molecular Dynamics Study and Natural Bond Orbital Analysis of HgC Coupling Constants

Bis-tetradentate complexes of Cd(ii) and Hg(ii) with N8coordination: structural and NMR comparisons

Prediction of NMR J-coupling in solids with the planewave pseudopotential approach

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Product

Resources

About

Bis-tetradentate complexes of Cd(ii) and Hg(ii) with N₈coordination: structural and NMR comparisons