An experimental and theoretical investigation into the binding interactions of silver cluster cations with ethene and propene

Manard, Manuel J.; Kemper, Paul R.; Bowers, Michael T.

doi:10.1016/j.ijms.2005.12.028

Cited by 19 publications

(9 citation statements)

References 53 publications

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“…Such a structural transformation has been proposed previously to occur for the adsorption of three ethylene ligands on Ag 5 + . 48,68 Our data clearly indicate that a similar geometric rearrangement is the explanation for the CO coverage dependent binding energies in the case of the silver-rich cluster complex Ag 4 Au(CO) q + (q = 1-6) (Fig. 4).…”

Section: Discussionsupporting

confidence: 59%

Composition dependent adsorption of multiple CO molecules on binary silver–gold clusters AgnAum+ (n + m = 5): theory and experiment

Popolan

Nößler

Mitrić

et al. 2010

Phys. Chem. Chem. Phys.

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The binding energies of multiple CO molecules to five-atom silver-gold cluster cations have been obtained employing temperature dependent gas phase ion trap measurements and ab initio calculations. The CO binding energies to Ag(n)Au(m)(+) (n + m = 5) decrease with increasing number of silver atoms. Most strikingly, after the adsorption of the fourth CO to Au(5)(+) and of the third CO to Ag(5)(+), respectively, a pronounced decrease in the binding energies of further CO molecules was observed. This is related to a CO-induced structural transformation yielding more compact metal cluster geometries. First principles calculations revealed that the exact structure of the carbonyl complexes with multiple CO and the nature of the CO-induced structural transformation strongly depend on the composition of the metal cluster as well as on the number of adsorbed CO molecules.

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Section: Discussionsupporting

confidence: 59%

Composition dependent adsorption of multiple CO molecules on binary silver–gold clusters AgnAum+ (n + m = 5): theory and experiment

Popolan

Nößler

Mitrić

et al. 2010

Phys. Chem. Chem. Phys.

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“…[29] Somewhat later also the weakly bound [AgA C H T U N G T R E N N U N G (C 2 H 4 ) y ] + (y = 3, 4) cations were observed in the MS; [30][31][32] computational studies also address these cations. [13,33] Over the last two years, the two missing [MA C H T U N G T R E N N U N G (h 2 -C 2 H 4 ) 3 ]…”

Section: -C H 4 ) 3 ]mentioning

confidence: 97%

Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)

Reisinger

Trapp

Knapp

et al. 2009

Chemistry A European J

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Compounds including the free or coordinated gas-phase cations [Ag(eta(2)-C(2)H(4))(n)](+) (n = 1-3) were stabilized with very weakly coordinating anions [A](-) (A = Al{OC(CH(3))(CF(3))(2)}(4), n = 1 (1); Al{OC(H)(CF(3))(2)}(4), n = 2 (3); Al{OC(CF(3))(3)}(4), n = 3 (5); {(F(3)C)(3)CO}(3)Al-F-Al{OC(CF(3))(3)}(3), n = 3 (6)). They were prepared by reaction of the respective silver(I) salts with stoichiometric amounts of ethene in CH(2)Cl(2) solution. As a reference we also prepared the isobutene complex [(Me(2)C=CH(2))Ag(Al{OC(CH(3))(CF(3))(2)}(4))] (2). The compounds were characterized by multinuclear solution-NMR, solid-state MAS-NMR, IR and Raman spectroscopy as well as by their single crystal X-ray structures. MAS-NMR spectroscopy shows that the [Ag(eta(2)-C(2)H(4))(3)](+) cation in its [Al{OC(CF(3))(3)}(4)](-) salt exhibits time-averaged D(3h)-symmetry and freely rotates around its principal z-axis in the solid state. All routine X-ray structures (2theta(max.) < 55 degrees) converged within the 3sigma limit at C=C double bond lengths that were shorter or similar to that of free ethene. In contrast, the respective Raman active C=C stretching modes indicated red-shifts of 38 to 45 cm(-1), suggesting a slight C=C bond elongation. This mismatch is owed to residual librational motion at 100 K, the temperature of the data collection, as well as the lack of high angular data owing to the anisotropic electron distribution in the ethene molecule. Therefore, a method for the extraction of the C=C distance in [M(C(2)H(4))] complexes from experimental Raman data was developed and meaningful C=C distances were obtained. These spectroscopic C=C distances compare well to newly collected X-ray data obtained at high resolution (2theta(max.) = 100 degrees) and low temperature (100 K). To complement the experimental data as well as to obtain further insight into bond formation, the complexes with up to three ligands were studied theoretically. The calculations were performed with DFT (BP86/TZVPP, PBE0/TZVPP), MP2/TZVPP and partly CCSD(T)/AUG-cc-pVTZ methods. In most cases several isomers were considered. Additionally, [M(C(2)H(4))(3)] (M = Cu(+), Ag(+), Au(+), Ni(0), Pd(0), Pt(0), Na(+)) were investigated with AIM theory to substantiate the preference for a planar conformation and to estimate the importance of sigma donation and pi back donation. Comparing the group 10 and 11 analogues, we find that the lack of pi back bonding in the group 11 cations is almost compensated by increased sigma donation.

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“…The homo- and heterolytic C–H bond cleavage (as well as functionalization) is well-known for its significance in chemistry and is regarded as a longstanding central challenge. − Metal cluster reactivity shows its own novelty in this topic. For example, considerable investigations have been conducted upon the activation of methane by gas-phase palladium model systems. − Experimental observations showed that neutral clusters Pd x ( x ≤ 24) tend to adsorb methane with a few exceptions (e.g., Pd 3 and Pd 4 ), while in contrast, the reactivity of small palladium oxides toward methane is size-dependent for methane dehydrogenation. , Recently, Bernhardt and co-workers showed an interesting study on the reactivity of methane with Pd x + ( x = 2–4) clusters.…”

Section: Metal Cluster Reactivities With Nonpolar Moleculesmentioning

confidence: 99%

Reactivity of Metal Clusters

2016

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We summarize here the research advances on the reactivity of metal clusters. After a simple introduction of apparatuses used for gas-phase cluster reactions, we focus on the reactivity of metal clusters with various polar and nonpolar molecules in the gas phase and illustrate how elementary reactions of metal clusters proceed one-step at a time under a combination of geometric and electronic reorganization. The topics discussed in this study include chemical adsorption, addition reaction, cleavage of chemical bonds, etching effect, spin effect, the harpoon mechanism, and the complementary active sites (CAS) mechanism, among others. Insights into the reactivity of metal clusters not only facilitate a better understanding of the fundamentals in condensed-phase chemistry but also provide a way to dissect the stability and reactivity of monolayer-protected clusters synthesized via wet chemistry.

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An experimental and theoretical investigation into the binding interactions of silver cluster cations with ethene and propene

Cited by 19 publications

References 53 publications

Composition dependent adsorption of multiple CO molecules on binary silver–gold clusters AgnAum+ (n + m = 5): theory and experiment

Composition dependent adsorption of multiple CO molecules on binary silver–gold clusters AgnAum+ (n + m = 5): theory and experiment

Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)

Reactivity of Metal Clusters

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An experimental and theoretical investigation into the binding interactions of silver cluster cations with ethene and propene

Cited by 19 publications

References 53 publications

Composition dependent adsorption of multiple CO molecules on binary silver–gold clusters AgnAum+ (n + m = 5): theory and experiment

Composition dependent adsorption of multiple CO molecules on binary silver–gold clusters AgnAum+ (n + m = 5): theory and experiment

Silver–Ethene Complexes [Ag(η2‐C2H4)n][Al(ORF)4] with n=1, 2, 3 (RF=Fluorine‐Substituted Group)

Reactivity of Metal Clusters

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Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)