Theoretical Chemistry of Gold – From Atoms to Molecules, Clusters, Surfaces and the Solid State

Schwerdtfeger, Peter; Lein, Matthias

doi:10.1002/9783527626724.ch4

Cited by 37 publications

(23 citation statements)

References 440 publications

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“…This result is consistent with the property of gold which has a tendency to form supramolecular architecture (aurophilicity) due to its unusually large relativistic 6 s-orbital stabilization (contraction) [56]. In addition, this observation is similar to the results of Cu ion-peptide complexes [34], which reports the detection of [peptide+xCu -(x -1)H] (x=1-6) ions.…”

Section: Resultssupporting

confidence: 88%

“…Several factors contribute to the efficacy of the identification of gold binding sites using the CID mass spectra. First, due to the large relativistic effect of gold [56], gold-peptide binding is relatively strong and survive the CID condition used here. Second, angiotensin I contains one Arg and two His basic residues equally distributed along the peptide chain, one Pro residue in the middle of the peptide chain, and one Asp residue.…”

Section: Resultsmentioning

confidence: 99%

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Gold Ion–Angiotensin Peptide Interaction by Mass Spectrometry

Lee

Jayathilaka

Gupta

et al. 2012

J. Am. Soc. Mass Spectrom.

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Stimulated by the interest in developing gold compounds for treating cancer, gold ionangiotensin peptide interactions are investigated by mass spectrometry. Under the experimental conditions used, the majority of gold ion-angiotensin peptide complexes contain gold in the oxidation states I and III. Both ESI-MS and MALDI-TOF MS detect singly/multiply charged ions for mononuclear/multinuclear gold-attached peptides, which are represented as [peptide+a Au (I)+b Au(III)+(e -a -3b) H] e+ , where a,b≥0 and e is charge. ESI-MS data shows singly/multiply charged ions of Au(I)-peptide and Au(III)-peptide complexes. This study reveals that MALDI-TOF MS mainly detects singly charged Au(I)-peptide complexes, presumably due to the ionization process. The electrons in the MALDI plume seem to efficiently reduce Au(III) to Au(I). MALDI also tends to enhance the higher polymeric forms of gold-peptide complexes regardless of the laser power used. Collision-induced dissociation experiments of the mononuclear and dinuclear gold-attached peptide ions for angiotensin peptides show that the gold ion (a soft acid) binding sites are in the vicinity of Cys (a soft ligand), His (a major anchor of peptide for metal ion chelation), and the basic residue Arg. Data also suggests that the abundance of gold-attached peptides increases with higher gold concentration until saturation, after which an increase in gold ion concentration leads to the aggregation and/or precipitation of gold-bound peptides.

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Section: Resultssupporting

confidence: 88%

Section: Resultsmentioning

confidence: 99%

Gold Ion–Angiotensin Peptide Interaction by Mass Spectrometry

Lee

Jayathilaka

Gupta

et al. 2012

J. Am. Soc. Mass Spectrom.

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“…The results for the monocyanides show a difference of 0.60 eV between AuCN and RgCN, whereas for the dicyanides the difference is very small. The bond dissociation energies for AuCN and AuðCNÞ 2 2 are in good agreement with the previously reported CCSD(T) and MP2 results [36] ; 3.85 eV and 4.27 eV for AuCN, respectively, and 4.37 eV and 4.72 eV, respectively for AuðCNÞ 2 2 (see Table 3). Overall, our results show that the Rg complexes behave like the Au complexes.…”

Section: Group 11: Gold and Roentgeniumsupporting

confidence: 79%

Darmstadtium, roentgenium, and copernicium form strong bonds with cyanide

Demissie

Ruud

2017

Int J of Quantum Chemistry

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We report the structures and properties of the cyanide complexes of three superheavy elements (darmstadtium, roentgenium, and copernicium) studied using two-and four-component relativistic methodologies. The electronic and structural properties of these complexes are compared to the corresponding complexes of platinum, gold, and mercury. The results indicate that these superheavy elements form strong bonds with cyanide. Moreover, the calculated absorption spectra of these superheavy-element cyanides show similar trends to those of the corresponding heavyatom cyanides. The calculated vibrational frequencies of the heavy-metal cyanides are in good agreement with available experimental results lending support to the quality of our calculated vibrational frequencies for the superheavy-atom cyanides.copernicium, darmstadtium, relativistic DFT, roentgenium, superheavy elements | I N TR ODU C TI ONThe term heavy atom refers roughly to elements in the fourth to sixth periods of the periodic table, whereas elements in the seventh period are called superheavy elements. Heavy-element compounds have been rather extensively studied [1][2][3][4][5][6][7] compared to the superheavy ones. This is due to the abundance of the heavy elements and the many uses of heavy-element compounds; for instance, gold dicyanide (AuðCNÞ 2 2 ) was used in gold mining, [8,9] platinum cyanides are used in nanomaterials, [10] whereas mercury(II) cyanide (HgðCNÞ 2 ) was used as an antiseptic [11] until this was stopped due to its toxicity. [12] In contrast, the lack of a natural abundance of the superheavy elements has limited the number of studies of compounds involving these superheavy elements. In particular, with the exception of RgCN, [6] there has been no studies of the cyanide complexes of Ds, Rg, and Cn reported previously in the literature. Patzschke and Pyykk€ o [13] studied the properties of darmstadtium carbonyl and carbide and compared them to platinum carbide and carbonyl and found that darmstadtium resembled platinum in its bonding properties. [13] Theoretical studies of darmstadtium hexafluoride (DsF 6 ) and darmstadtium tetrachloride (DsCl 4 ) have also been reported and these compounds have been shown to have properties similar to those of the lighter group analogues. [14][15][16] The structure and bonding properties of roentgenium monocyanide have been compared with the cyanides of copper, silver, and gold. [6] Theoretical studies on the electronic structures of RgX (X 5 H, F, Cl, Br, O, Au, or Rg) have also been reported [5] where the RgAH bond in RgH was found to be strong due to relativistic effects, 153.0 pm using ZORA and 150.3 pm using spin-orbit pseudopotential coupled cluster calculations, in contrast to 190.8 pm using nonrelativistic calculations (a 27% relativistic bond-length contraction). Calculations using two-component spin-orbit-coupled relativistic energy-adjusted pseudopotentials showed that the CnAH bond length in CnH 1 is shorter than the ZnAH bond length in ZnH 1 . [17] The calculated equilibrium bond d...

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“…5 CuCN was also compared to the CuNC isomer at the CCSD(T) level using scalar relativistic effects, with the former found to be 11.5 kcal mol -1 lower in energy. 9 These studies have superseded a number of earlier, somewhat lower-level calculations, 4,[10][11][12] although all are in agreement that these molecules are linear with 1 Σ + electronic ground states.…”

Section: Introductionmentioning

confidence: 90%

Ab initio ro-vibrational spectroscopy of the group 11 cyanides: CuCN, AgCN, and AuCN

Hill

Mitrushchenkov

Peterson

2013

The Journal of Chemical Physics

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Accurate near-equilibrium potential energy and dipole moment functions have been calculated for the linear coinage-metal cyanides CuCN, AgCN, and AuCN using coupled cluster methods and sequences of correlation consistent basis sets. The explicitly correlated CCSD(T)-F12b method is used for the potential energy surfaces (PESs) with inclusion of core correlation, and is combined with contributions from molecular spinorbit coupling, scalar relativity, and effects due to higher order electron correlation. The resulting composite PESs are used in both perturbative and variational calculations of the ro-vibrational spectra. In addition to accurate equilibrium geometries, the ro-vibrational spectra are predicted, which are found to be relatively intense in the 200 -600 cm -1 range due to the bending and metal-carbon stretching modes. The CN stretch near 2165 cm -1 is also predicted to carry enough intensity to allow its observation by experiment. A strong Fermi-resonance is predicted between the first overtone of the bend and the fundamental of the metal-carbon stretch for both CuCN and AgCN. The heats of formation at 0 K are predicted from their calculated atomization energies to be 89.8, 88.6, and 104.5 kcal mol -1 for CuCN, AgCN, and AuCN, respectively. † email addresses: grant. hill@glasgow.ac.uk, Alexander.Mitrushchenkov@univ-mlv.fr, kipeters@wsu.edu 2

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Theoretical Chemistry of Gold – From Atoms to Molecules, Clusters, Surfaces and the Solid State

Cited by 37 publications

References 440 publications

Gold Ion–Angiotensin Peptide Interaction by Mass Spectrometry

Gold Ion–Angiotensin Peptide Interaction by Mass Spectrometry

Darmstadtium, roentgenium, and copernicium form strong bonds with cyanide

Ab initio ro-vibrational spectroscopy of the group 11 cyanides: CuCN, AgCN, and AuCN

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