Communication: CO oxidation by silver and gold cluster cations: Identification of different active oxygen species

Popolan, Denisia; Bernhardt, Thorsten M.

doi:10.1063/1.3563631

Cited by 26 publications

(29 citation statements)

References 33 publications

(23 reference statements)

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“…[15] The [Au 3 ] + -catalyzed oxidation of CO has been studied theoretically, [16] and [Au 3 ] + in the gas phase has been shown to mediate the oxidation of CO by N 2 O. [17] Mass spectrometry studies suggest that a transient [L 2 Au 3 ] + ion, where L 2 is a bridging bisphosphine, undergoes oxidative addition with aryl iodides. [18] Cluster complexes featuring the cyclo-Au 3 moiety bonded to tungsten [19] or to main-group elements [20] are known, as are triangular [Au 2 M] clusters.…”

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confidence: 99%

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H₃]⁺

et al. 2012

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The ion [H 3 ] + represents a classic case in molecular orbital theory, the simplest three-center, two-electron bond. [1] The proton affinity of dihydrogen in the gas phase, at 4.4 eV, [2] is nearly equal to the bond enthalpy of H 2 itself. [3] The [H 3 ] + ion has been studied spectroscopically in the laboratory; [4] it has been detected in planetary atmospheres, [5a] and is notably abundant in interstellar space. [5b] The concept of isolobality has been used extensively to draw analogies between [LAu] + and [H] + , [6] and after the discovery of isolable [(LAu) 2 H] + complexes, [7,8] we became interested in the synthesis of an allgold analogue of [H 3 ] + .Complexes of gold(I) with atoms such as oxygen and the heavier chalcogens, nitrogen, and carbon, often exhibit weak but important aurophilic interactions between the d 10 metal centers. [9] Multicenter covalent bonding is observed in formally mixed-valent gold(I)/gold(0) clusters. [10] These include edge-sharing bitetrahedral clusters of the general formula [(LAu) 6 ] 2+ , [11] and tetrahedral clusters of the formula [(LAu) 4 ] 2+ . [12] Clusters such as [(LAu) 6 ] 2+ , (L 6 Au 8 ) 2+ , and [(LAu) 4 ] 2+ , have been synthesized by the reduction of phosphine-supported m 3 -oxo or m 3 -imido cations with carbon monoxide. [13] Whereas gold(II) dimers form covalent goldgold bonds through the interaction of half-filled d-orbitals, [14] the gold-gold bonding in mixed-valent gold(I)/gold(0) clusters [(LAu) n ] x+ arises to an important extent from symmetryadapted combinations of partially filled gold 6 s orbitals. [10b] The interaction of small gold clusters and nanoparticles with O 2 has been studied as a key step in aerobic oxidation catalysis. [15] The [Au 3 ] + -catalyzed oxidation of CO has been studied theoretically, [16] and [Au 3 ] + in the gas phase has been shown to mediate the oxidation of CO by N 2 O. [17] Mass spectrometry studies suggest that a transient [L 2 Au 3 ] + ion, where L 2 is a bridging bisphosphine, undergoes oxidative addition with aryl iodides. [18] Cluster complexes featuring the cyclo-Au 3 moiety bonded to tungsten [19] or to main-group elements [20] are known, as are triangular [Au 2 M] clusters. [21] We now report the characterization of a stable [(LAu) 3 ] + complex, where L is the N-heterocyclic carbene (NHC) 1,3bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IDipp). Density functional theory (DFT) lends insight into the bonding among gold centers. Preliminary studies demonstrate sluggish reactivity with oxygen-atom-transfer agents, but facile reactivity with soft electrophiles.Initially, we planned to obtain [(LAu) 3 ] + through the reduction of a corresponding m 3 -oxo complex [(LAu) 3 O] + . A wide range of phosphorus-based donor ligands support complexes of this type. [22] Our efforts to obtain an analogous NHC-supported species by the established routes gave rise to mixtures of products, including the hydroxide-bridged digold cation [(LAu) 2 OH] + . [23] Reasoning that the formation of strong silicon-heteroatom bonds co...

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Synthesis of a Trigold Monocation: An Isolobal Analogue of [H₃]⁺

et al. 2012

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“…The interaction of small gold clusters and nanoparticles with O 2 has been studied as a key step in aerobic oxidation catalysis 15. The [Au 3 ] + ‐catalyzed oxidation of CO has been studied theoretically,16 and [Au 3 ] + in the gas phase has been shown to mediate the oxidation of CO by N 2 O 17. Mass spectrometry studies suggest that a transient [L 2 Au 3 ] + ion, where L 2 is a bridging bisphosphine, undergoes oxidative addition with aryl iodides 18.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H₃]⁺

et al. 2012

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Isolobal und isolierbar: Ein dreieckiges [L3Au3]+‐Ion mit N‐heterocyclischen Carbenliganden L wurde kristallographisch charakterisiert (siehe Struktur; Au gelb, C grau, N blau). Dichtefunktionalrechnungen deuten auf eine vollständige Valenzdelokalisierung über die Goldatome hin, wobei sich das HOMO vor allem aus Gold‐6s‐Orbitalen zusammensetzt und das LUMO als entartetes Paar vorliegt. Diese Orbitalstruktur ist derjenigen von [H3]+ analog.

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“…(34)). Au À was unreactive towards CF 3 CO 2 H: The bare gold cluster anions Au 2 À and Au 3 À , are able to form co-adsorption complexes, Au a À (CO) b (O) c (a ¼ 2, 3; b ¼ 1; c ¼ 1, 2), when exposed to small partial pressure of CO and O 2 in a temperature-controlled ion trap at cryogenic temperatures [287]. This type of cluster complex has been proposed theoretically to be a key intermediate in a catalytic CO oxidation cycle [288].…”

Section: Reactions With Other Neutral Substratesmentioning

confidence: 99%

“…In the first step, Fe + reacted with N 2 O by oxygen atom transfer to yield FeO + , which transferred an oxygen atom to CO in the second step to yield neutral CO 2 and regenerate the atomic Fe + catalyst. The exploration of gas-phase transition-metal catalytic cycles has continued in the intervening 4 decades and been reviewed on several occasions [28,29,287,322,323]. Here we focus on complete gas-phase catalytic cycles that are catalysed by gold nanoclusters.…”

Section: Catalysis By Gold Cluster Ionsmentioning

confidence: 99%

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Gas Phase Formation, Structure and Reactivity of Gold Cluster Ions

Zavras

Khairallah

O’Hair

2014

Structure and Bonding

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With the advent of electrospray ionisation (ESI) and matrix-assisted laser desorption ionisation (MALDI), mass spectrometry (MS) is now routinely used to establish the molecular formulae of gold nanoclusters (AuNCs). ESI-MS has been used to monitor the solution phase growth of AuNCs when gold salts are reduced in the presence of phosphine or thiolate ligands. Beyond this analytical role, over the past 2 decades MS-based methods have been employed to examine the fundamental properties and reactivities of AuNC ions. For example, ion mobility and spectroscopic measurements may be used to assign structures; thermochemical data provides important information on ligand binding energies; unimolecular chemistry can be explored; and ion-molecule reactions with various substrates can be used to probe catalysis by AuNC ions. MS can also be used to monitor and direct the synthesis of AuNC bulk material either by guiding solution phase synthesis conditions or by soft landing a beam of mass-selected (i.e. monodisperse) AuNC ions onto a surface. This review showcases all areas in which mass spectrometry has played a role in AuNC science.

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Communication: CO oxidation by silver and gold cluster cations: Identification of different active oxygen species

Abstract: Strongly cluster size dependent reaction behavior of CO with on free silver cluster anions

Cited by 26 publications

References 33 publications

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H₃]⁺

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H₃]⁺

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H₃]⁺

Gas Phase Formation, Structure and Reactivity of Gold Cluster Ions

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Communication: CO oxidation by silver and gold cluster cations: Identification of different active oxygen species

Abstract: Strongly cluster size dependent reaction behavior of CO with on free silver cluster anions

Cited by 26 publications

References 33 publications

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H3]+

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H3]+

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H3]+

Gas Phase Formation, Structure and Reactivity of Gold Cluster Ions

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Synthesis of a Trigold Monocation: An Isolobal Analogue of [H₃]⁺

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H₃]⁺

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H₃]⁺