Structure and bonding of the MCN molecules, M=Cu,Ag,Au,Rg

Zaleski‐Ejgierd, Patryk; Patzschke, Michael; Pyykkö, Pekka

doi:10.1063/1.2937148

Cited by 29 publications

(49 citation statements)

References 20 publications

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“…Our AuAC bond length falls inbetween the result obtained preivously for AuCN using MP2/cc-pVQZ (186.51 pm) and using CCSD(T)/cc-pVQZ/191.05 pm). [6] In both AuCN and RgCN, the metal-carbon bonds show multiple bond character, all considerably shorter than the sum of the single-bond atomic radii reported by Pyykk€ o. [34] For instance, in AuCN the sum of the single-bond atomic radii between Au and C is 199.00 pm, 9.82 pm longer than our calculated DKS/PBE/dyall-cvtz bond length.…”

Section: Group 11: Gold and Roentgeniummentioning

confidence: 56%

“…[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.…”

mentioning

confidence: 99%

“…[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 .…”

Section: Introductionmentioning

confidence: 99%

“…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.…”

Section: Introductionmentioning

confidence: 99%

“…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.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Group 11: Gold and Roentgeniummentioning

confidence: 56%

mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Darmstadtium, roentgenium, and copernicium form strong bonds with cyanide

Demissie

Ruud

2017

Int J of Quantum Chemistry

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Gas Phase Chemistry of Gold

Rappoport

Weber²

2014

Patai's Chemistry of Functional Groups

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This chapter deals with results from gas phase experiments on mononuclear gold compounds, although there will not be too much discussion of gold in an organic chemistry context. Mass spectrometry in combination with laser spectroscopic techniques has made a wealth of experimental data on gold complexes available. Such experiments can yield deep and detailed insight into the chemistry of gold, since the target systems are very well defined and circumvent the difficulties associated with solvent interaction and speciation that complicate many experiments in condensed phase environments. Moreover, gas phase experiments can serve to validate computational and theoretical approaches to gold chemistry. We discuss experimental approaches to bring gold compounds into the gas phase, and we showcase data on complexes with atomic and molecular ligands, as well as studies on the reactivity of gold ions.

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The Dinitrogen‐Ligated Triaurum Cation, Aurodiazenylium, Auronitrenium, Auroammonia, and Auroammonium

Liang

Qin

et al. 2011

Angewandte Chemie

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Gold complexes and nanoparticles exhibit fascinating properties and have found various applications recent years. [1, 2] The chemistry of gold, significantly different from that of its congeners (silver and copper), is mostly dominated by its extraordinarily strong relativistic effects, [3] which impose a very small energy gap between its 5d and 6s valence orbitals and, consequently, a high degree of sd hybridization as well as an even higher electronegativity than that of the nonmetal monovalent hydrogen, that is, Au 2.54 versus H 2.20 (Pauling scale). [4] The concept of gold-hydrogen analogy thus emerged [5] and has been extensively exploited in synthetic chemistry. [1,6] Since the isolobal analogy [7] between phosphine-ligated gold (AuPR 3 ) and hydrogen (H) was noticed by Mingos [5a] in mid 1970s, the use of the AuPR 3 synthon has brought out to a large number of Au-containing metal cluster compounds. [1,6] Key examples are [O(AuPPh 3 ) n ] (nÀ2)+ (n = 3,4), [8] [N(AuPPh 3 ) n ] (nÀ3)+ (n = 4, 5), [9] [C(AuPPh 3 ) n ] (nÀ4)+ (n = 4-6), [10] and [N 2 (AuPR 3 ) 6 ] 2+ , [11] which are analogous to [OH n ] (nÀ2)+ (n = 3,4), [NH n ] (nÀ3)+ (n = 4, 5), [CH n ] (nÀ4)+ (n = 4-6), and hydrazinium [H 3 N À NH 3 ] 2+ , respectively. On the other hand, a simple gold-hydrogen analogy was recently observed in a series of binary Si/Au clusters [Si m Au n ] (m = 1,2; n = 2-4) in the gas phase by Wang and co-workers. [12] Herein we report a joint experimental and theoretical investigation on a series of abundant Au/N binary cluster cations, [AuN 4 ] + , [Au n N 2n+1 ] + (n = 2-4), and [Au 3 N 6 ] + , which exist as dinitrogen-ligated aurodiazenylium [(N 2 (AuN 2 )] + , auronitrenium [N(AuN 2 ) 2 ] + , auroammonia radical cation [N(AuN 2 ) 3 ] + , auroammonium [N(AuN 2 ) 4 ] + , and triaurum cation [(AuN 2 ) 3 ] + , and are struc-turally and electronically analogous to diazenylium ([N 2 H] + ), [13] nitrenium ([NH 2 ] + ), [14] ammonia radical cation ([NH 3 ] + ), [15] ammonium ([NH 4 ] + ), and trihydrogen cation ([H 3 ] + ), [16] respectively, by following the isolobal analogy between N 2 -ligated gold (AuN 2 ) and hydrogen. The chemical stability of these N 2 -ligated complexes suggests that they might be viable in wet chemistry. Such a N 2 -assisted goldhydrogen analogy involving a [AuN 2 ] + synthon and covalent dative Au + ÀN 2 bond is also relevant to the industrially important nitrogen fixation. Figure 1 displays the mass spectrum (180 < m/e < 1000 amu) of [Au p N q ] + clusters obtained by reactive collision of N 2 with laser-vaporized gold clusters. The strong mass spectral peaks for [AuN 4 ] + , [Au 2 N 5 ] + , [Au 3 N 6 ] + , and [Au 4 N 9 ] + indicate that these "magic-number" cations are the most abundant for the positive cluster distribution. Furthermore, the signal intensity of [Au 3 N 7 ] + , a radical cation, is comparable to that of [Au 2 N 5 ] + , likely owing to the high stability of its neutral form, Au 3 N 7 . Moreover, the intense signals of [Au m N (2m+1) ] + (m = 2-4) with odd numbers of N atom...

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Structure and bonding of the MCN molecules, M=Cu,Ag,Au,Rg

Cited by 29 publications

References 20 publications

Darmstadtium, roentgenium, and copernicium form strong bonds with cyanide

Darmstadtium, roentgenium, and copernicium form strong bonds with cyanide

Gas Phase Chemistry of Gold

The Dinitrogen‐Ligated Triaurum Cation, Aurodiazenylium, Auronitrenium, Auroammonia, and Auroammonium

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