On the relation between germanium-73 and other main group IV element NMR chemical shifts

Watkinson, Philip; Mackay, K. M.

doi:10.1016/0022-328x(84)80575-6

Cited by 30 publications

(13 citation statements)

References 11 publications

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“…The problem with this last element is that there are not enough experimental chemical shifts available for the simplest lead centered tetrahalides, in order to apply our procedure. Fortunately reasonable correlations among NMR chemical shifts of different elements belonging to the fourth main group of the Periodic Table were found. , In this manner the NMR analysis of tin- and lead-containing molecules can usually be made together. Wrackmeyer published a series of review articles with a large amount of chemical shift data for Sn- and Pb-containing compounds. − On the basis of experimental measurements, a linear relationship between the chemical shifts of Sn(IV) and Pb(IV) for comparable tin and lead compounds was proposed. , We should emphasize here that tin chemical shifts cover a range of approximately 6500 ppm, from +4000 to −2500 ppm, using tetramethyltin, Sn(CH 3 ) 4 , as a reference, and 207 Pb chemical shift covers a range of approximately 17000 ppm, from +11000 to −6000 ppm with tetramethyllead, Pb(CH 3 ) 4 , as a reference.…”

Section: Introductionmentioning

confidence: 97%

“…Fortunately reasonable correlations among NMR chemical shifts of different elements belonging to the fourth main group of the periodic table were found. 16,17 In this manner the NMR analysis of tin and lead containing molecules can usually be made together. Bern Wrackmeyer published a serie of review articles with a large amount of chemical shifts data for Sn and Pb containing compounds.…”

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confidence: 99%

“…This option was based on previous studies [17,18,19] which indicated that relativistic corrections to the exchange-correlation functionals have a negligible effect on spectroscopic constants that do not depend on the core.…”

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confidence: 99%

“…a : Experimental data taken from ref 17. The Journal of Physical Chemistry AArticle dx.doi.org/10.1021/jp502543m | J. Phys.…”

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Relativistic and Electron-Correlation Effects on the Nuclear Magnetic Resonance Shieldings of Molecules Containing Tin and Lead Atoms

Maldonado

Aucar

2014

J. Phys. Chem. A

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The reference values for NMR magnetic shieldings, σ ref , are of highest importance when theoretical analysis of chemical shifts are envisaged. The fact that the non relativistically valid relationship among spin-rotation constants and magnetic shieldings is not any longer valid for heavy atoms makes that the search for σ ref for such atoms needs new strategies to follow.We present here results of σ ref that were obtained applying an own simple procedure which mix accurate experimental chemical shifts (δ) and theoretical magnetic shieldings (σ). We calculated σ(Sn) and σ(Pb) in a family of heavy-halogen containing molecules.We found out that σ ref (Sn; Sn(CH 3 ) 4 ) in gas phase should be close to 3864.11 ± We studied tin and lead shieldings of the XY 4−n Z n (X = Sn, Pb; Y , Z = H, F, Cl, Br, I) and PbH 4−n I n (n = 0, 1, 2, 3, 4) family of compounds with four-component functionals as implemented in the DIRAC code. For these systems results of calculations with RelPPA-RPA are more reliable than the DFT ones. We argue on why those DFT functionals must be modified in order to obtain more accurate results of NMR magnetic shieldings within the relativistic regime: first, there is a dependence among both, electron correlation and relativistic effects that should be introduced in some way in the functionals; and second, the DIRAC code uses standard non-relativistic functionals and the functionals B3LYP and PBE0 were parameterized only with data taken from light elements. It can explain why they are not able to properly introduce relativistic effects on nuclear magnetic shieldings.We finally show that in the analysis of magnetic shieldings for the family of compounds mentioned above, one must consider the newest and so called heavy-atom effect on vicinal heavy atoms, HAVHA. Such effects are among the most important relativistic effects in these kind of compounds.

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Section: Introductionmentioning

confidence: 97%

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confidence: 99%

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confidence: 99%

“…a : Experimental data taken from ref 17. The Journal of Physical Chemistry AArticle dx.doi.org/10.1021/jp502543m | J. Phys.…”

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confidence: 99%

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Relativistic and Electron-Correlation Effects on the Nuclear Magnetic Resonance Shieldings of Molecules Containing Tin and Lead Atoms

Maldonado

Aucar

2014

J. Phys. Chem. A

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“…Several studies have been directed at the correlation of 73 Ge NMR chemical shifts with those of the other group 14 elements, specifically 29 Si and 119 Sn, and several correlation equations have been developed. The comparison of NMR data for 29 pairs of analogous silicon and germanium compounds and 26 pairs of analogous germanium and tin compounds was reported in 1984 [59], and two correlation equations were derived are shown as follows:…”

Section: Isrn Spectroscopymentioning

confidence: 99%

G73e Nuclear Magnetic Resonance Spectroscopy of Germanium Compounds

Weinert

2012

ISRN Spectroscopy

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The field of G73e NMR spectroscopy is reviewed in this paper, from early developments in the 1950s to present day research. Specific attention is paid to recent investigations, including the observation of fluxional behavior of hypervalent germanium species having five or six attached ligands by 73Ge NMR spectroscopy, the spectral properties of linear and branched oligogermanes that contain single germanium-germanium bonds, and the relatively new field of solid-state germanium-73 NMR.

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