1J(199Hg199Hg) values of up to 284 kHz in complexes of [Hg–Hg]2+ with crown ethers: the largest indirect coupling constants

Malleier, Richard; Kopacka, Holger; Schuh, Walter; Wurst, Klaus; Péringer, Paul

doi:10.1039/b007581g

Cited by 30 publications

(25 citation statements)

References 4 publications

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“…This can be rationalized by a simple argument based on Hückel theory [62]. For the complex of Hg 2þ 2 with the crown ethers 18-crown-6 and 15-crown-5, very good agreement with the experimental 1 J(Hg-Hg) of 284 kHz ( 199 Hg) [7] could be achieved. This is currently the largest experimentally determined coupling constant.…”

Section: Two-component Zora-dft Calculationsmentioning

confidence: 68%

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Relativistic Calculations of Spin–Spin Coupling Constants of Heavy Nuclei

Autschbach

Ziegler

2004

Calculation of NMR and EPR Parameters

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Section: Two-component Zora-dft Calculationsmentioning

confidence: 68%

“…The left complex (mixed 18-crown-6 and 15-crown-5) has been computed based on the crystal structure of Ref. [7], the right one (both 18-crown-6) based on an optimized geometry Ref. [28]; MCSCF-pPSO Ref.…”

Section: Coupling Anisotropiesmentioning

confidence: 99%

Relativistic Calculations of Spin–Spin Coupling Constants of Heavy Nuclei

Autschbach

Ziegler

2004

Calculation of NMR and EPR Parameters

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“…To the author's knowledge, a complex of Hg 2 2 + with the crown ethers 18-crown-6 and 15-crown-5, which has an experimental 1 JA C H T U N G T R E N N U N G (HgÀHg) of 284 kHz ( 199 Hg) [41] still holds the record for the largest experimentally determined J-coupling constant. In previous work, we have employed scalar relativistic point-nucleus computations with a local density functional and a JCPLtype basis (but with a highest exponent around 5 10 3 ) for Hg to obtain a calculated J-coupling of 278 kHz.…”

Section: Hg 2 2 +mentioning

confidence: 98%

“…Experimental structure of the Hg 2 2 + complex with 15-crown-5 and 18-crown-6. [41] Hydrogens omitted for clarity. Table 3.…”

Section: Wwwchemphyschemorgmentioning

confidence: 99%

Magnitude of Finite‐Nucleus‐Size Effects in Relativistic Density Functional Computations of Indirect NMR Nuclear Spin–Spin Coupling Constants

Autschbach

2009

ChemPhysChem

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A spherical Gaussian nuclear charge distribution model has been implemented for spin-free (scalar) and two-component (spin-orbit) relativistic density functional calculations of indirect NMR nuclear spin-spin coupling (J-coupling) constants. The finite nuclear volume effects on the hyperfine integrals are quite pronounced and as a consequence they noticeably alter coupling constants involving heavy NMR nuclei such as W, Pt, Hg, Tl, and Pb. Typically, the isotropic J-couplings are reduced in magnitude by about 10 to 15 % for couplings between one of the heaviest NMR nuclei and a light atomic ligand, and even more so for couplings between two heavy atoms. For a subset of the systems studied, viz. the Hg atom, Hg(2) (2+), and Tl--X where X=Br, I, the basis set convergence of the hyperfine integrals and the coupling constants was monitored. For the Hg atom, numerical and basis set calculations of the electron density and the 1s and 6s orbital hyperfine integrals are directly compared. The coupling anisotropies of TlBr and TlI increase by about 2 % due to finite-nucleus effects.

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“…The structure of (I) represents a rare example of a watercoordinated Hg 2 system, this feature having been previously documented only in the black 3-pyridylsulfonate (Brodersen et al, 1980) and the colourless methanesulfonate (Malleier et al, 2001) complexes.…”

Section: Commentmentioning

confidence: 92%

Poly[bis[aquamercury(I)]-di-μ-aqua-μ-1,5-naphthalenedisulfonato]

et al. 2005

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In the crystal structure of the title polymeric complex, [Hg2(C10H6O6S2)(H2O)4]n, the metal atom of an H2O→Hg⋯Hg←H2O unit [Hg←Owater = 2.124 (7) Å] is linked to the metal atom of an adjacent unit by two water molecules [Hg←Owater = 2.619 (7) and 2.872 (7) Å], giving rise to a polycationic chain. Adjacent chains are linked through the dianion via a weaker interaction [Hg⋯Osulfonate = 3.062 (7) Å] to form layers. The H2O→Hg⋯Hg←H2O unit, the (H2O→Hg)2 parallelogram and the dianion all lie on centres of inversion. Hydrogen bonding consolidates the layers of the structure into a three‐dimensional network architecture.

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1J(199Hg199Hg) values of up to 284 kHz in complexes of [Hg–Hg]2+ with crown ethers: the largest indirect coupling constants

Abstract: The values of the 1 J( 199 Hg 199 Hg) coupling constant in solution of the asymmetric dimercury(2+) complexes with the stoichiometries Hg 2 2+ /18-crown-6 and Hg 2 2+ /18-crown-6/15-crown-5 are 220 300 and 284 100 Hz, respectively, representing the largest scalar couplings measured.

Cited by 30 publications

References 4 publications

Relativistic Calculations of Spin–Spin Coupling Constants of Heavy Nuclei

Relativistic Calculations of Spin–Spin Coupling Constants of Heavy Nuclei

Magnitude of Finite‐Nucleus‐Size Effects in Relativistic Density Functional Computations of Indirect NMR Nuclear Spin–Spin Coupling Constants

Poly[bis[aquamercury(I)]-di-μ-aqua-μ-1,5-naphthalenedisulfonato]

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