ESCA and Mössbauer study of compounds of gold in the oxidation states +I, +II, and +III

Schmidbaur, H.; Mandl, Johann R.; Wagner, Fritz; Vondel, D.F. van de; Kelen, G.P. Van Der

doi:10.1039/c39760000170

Cited by 36 publications

(6 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The ESCA spectrum of the mixed valence complex is supportive of the presence of the + 1 and + 3 oxidation states. The mixed valence complex produces a Au(4fT/2) line at a binding energy of 87.1 eV which can be assigned to the + 3 oxidation state and another line at 84.9 eV which can be assigned to the + 1 state [7][8][9]. The spectrum of the Au(III) complex, trichloro(dimethyl sulfoxide)Au(III), also has a line at a binding energy of 87.1eV while gold metal, as a reference, has its Au(4fT/2) line at 83.8 eV.…”

Section: Resultsmentioning

confidence: 99%

A mixed valence complex of gold with dimethyl sulfoxide

Schoenfelner

Potts

1981

Journal of Inorganic and Nuclear Chemistry

View full text Add to dashboard Cite

equilibrium constant Km of PbHL 2+ among the four amino acids. If the binding of Pb 2. through the carboxylate group occurs in PbHL 2÷, as was suggested previously [l], this trend is consistent with the fact that no difference in proton affinity of the carboxylate groups of the zwitter-ions is observed among the amino acids. On the contrary, it is obvious that the equilibrium constants/31o~ of the three C-substituted derivatives are smaller than that of glycine in spite of the increased basicity (Kt) of the nitrogen in the derivatives compared with glycine.The distribution of the species as a function of -log[H +] calculated at Cpb = 0.005 mol dm 3 and CL = 0.05 mol dm 3 using their constants are drawn in Fig. 5.

show abstract

Section: Resultsmentioning

confidence: 99%

A mixed valence complex of gold with dimethyl sulfoxide

Schoenfelner

Potts

1981

Journal of Inorganic and Nuclear Chemistry

View full text Add to dashboard Cite

show abstract

“…This observation is somewhat surprising but in agreement with previous results on dinuclear gold complexes with o-metallated phosphines or phosphorous diylides. In these last cases 31 P NMR spectra and XPS analysis suggest a similar electron density on gold(II) and gold(III) centres [12,13].…”

Section: Synthesis Of Gold(iii) Di(nhc) Complexesmentioning

confidence: 93%

Synthesis of dinuclear N-heterocyclic dicarbene Au(III)/Au(III) and Au(II)/Au(II) complexes via oxidative addition of chlorine or bromine to Au(I)/Au(I) species

Baron

Tubaro

Basato

et al. 2012

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

“…[132][133][134][135][136] and references therein). Aiming at a comprehensive assessment, one could furthermore take into account complexes of Mössbauer active isotopes such as 127 I or 129,131 Xe for which it would be interesting to study the p 1/2 contributions to the relative shift.…”

Section: Discussionmentioning

confidence: 99%

Mössbauer spectroscopy for heavy elements: a relativistic benchmark study of mercury

Knecht

Fux

Meer³

et al. 2011

Theor Chem Acc

View full text Add to dashboard Cite

The electrostatic contribution to the Mössbauer isomer shift of mercury for the series HgF n (n = 1, 2, 4) with respect to the neutral atom has been investigated in the framework of four-and two-component relativistic theory. Replacing the integration of the electron density over the nuclear volume by the contact density (that is, the electron density at the nucleus) leads to a 10% overestimation of the isomer shift. The systematic nature of this error suggests that it can be incorporated into a correction factor, thus justifying the use of the contact density for the calculation of the Mössbauer isomer shift. The performance of a large selection of density functionals for the calculation of contact densities has been assessed by comparing with finite-field four-component relativistic coupled-cluster with single and double and perturbative triple excitations [CCSD(T)] calculations. For the absolute contact density of the mercury atom, the Density Functional Theory (DFT) calculations are in error by about 0.5%, a result that must be judged against the observation that the change in contact density along the series HgF n (n = 1, 2, 4), relevant for the isomer shift, is on the order of 50 ppm with respect to absolute densities. Contrary to previous studies of the 57 Fe isomer shift (F Neese, Inorg Chim Acta 332:181, 2002), for mercury, DFT is not able to reproduce the trends in the isomer shift provided by reference data, in our case CCSD(T) calculations, notably the non-monotonous decrease in the contact density along the series HgF n (n = 1, 2, 4). Projection analysis shows the expected reduction of the 6s 1/2 population at the mercury center with an increasing number of ligands, but also brings into light an opposing effect, namely the increasing polarization of the 6s 1/2 orbital due to increasing effective charge of the mercury atom, which explains the nonmonotonous behavior of the contact density along the series. The same analysis shows increasing covalent contributions to bonding along the series with the effective charge of the mercury atom reaching a maximum of around ?2 for HgF 4 at the DFT level, far from the formal charge ?4 suggested by the oxidation state of this recently observed species. Whereas the geometries for the linear HgF 2 and square-planar HgF 4 molecules were taken from previous computational studies, we optimized the equilibrium distance of HgF at the four-component Fock-space CCSD/aug-cc-pVQZ level, giving spectroscopic constants r e = 2.007 Å and x e = 513.5 cm -1 .Dedicated to Professor Pekka Pyykkö on the occasion of his 70th birthday and published as part of the Pyykkö Festschrift Issue.Electronic supplementary material The online version of this article

show abstract

ESCA and Mössbauer study of compounds of gold in the oxidation states +I, +II, and +III

Cited by 36 publications

References 0 publications

A mixed valence complex of gold with dimethyl sulfoxide

A mixed valence complex of gold with dimethyl sulfoxide

Synthesis of dinuclear N-heterocyclic dicarbene Au(III)/Au(III) and Au(II)/Au(II) complexes via oxidative addition of chlorine or bromine to Au(I)/Au(I) species

Mössbauer spectroscopy for heavy elements: a relativistic benchmark study of mercury

Contact Info

Product

Resources

About