Mass Spectrometric Investigations of the Dissociation of [C@W6Cl17]− Ions in the Gas Phase

Burgert, Ralf; Koch, Katharina; Schnöckel, Hansgeorg; Weisser, Martina; Meyer, H.‐Jürgen

doi:10.1002/anie.200460972

Cited by 10 publications

(4 citation statements)

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“…This redox behavior has been observed before for analogous [W 6 Cl 18 ] and [W 6 CCl 18 ] hexametallic cluster compounds and is assumed to take place in the mass spectrometer. [16] On the other hand, formation of "[Nb 6 Cl 16 ]" species by losing chlorine atoms has been proposed to happen in heating processes of cluster precursors. [4b] Furthermore, the spectra of 1 and 3 reveal minor peaks centered at m/z = 1160, 1125, and 1087.…”

Section: Articlementioning

confidence: 99%

Hexanuclear Niobium Cluster Compounds with Protonated N‐Base Cations

König

Dartsch

Sperlich

et al. 2020

Zeitschrift anorg allge chemie

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Octahedral clusters of the [M 6 X 12 ] type offer numerous possibilities to form structural arrangements through different choices of bonding situations. In this paper a series of new cluster compounds of the transition metal niobium is described, which consist of the [Nb 6 Cl 18 ] 2-, and in one case [Nb 6 Cl 18 ] 3-, anion and protonated N-base cations ([MIm-H] + , [nPr 3 N-H] + , [TMGu-H] + , and [Tzn-H] +). They all are prepared using water scavenger compounds [SOCl 2 or (Ac) 2 O] under oxidising conditions, resulting in two-electron (or one-electron, respectively) oxidized cluster units with respect to the starting material [Nb 6 Cl 14 (H 2 O) 4 ]•4H 2 O. Of five members of this group single-crystal

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Section: Articlementioning

confidence: 99%

Hexanuclear Niobium Cluster Compounds with Protonated N‐Base Cations

König

Dartsch

Sperlich

et al. 2020

Zeitschrift anorg allge chemie

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“…Therefore, we started with a chemically rather inert C@W 6 Cl 18 cluster anion containing a carbon atom in the centre of its W 6 cage. 22,36,37 After these experiments had demonstrated that our ESI source was basically suitable for the realization of such investigations, we intended to use this route for transferring the metalloid cluster ion [Ga 13 (GaR) 6 ] À 4,21 from the solution to the gas phase. Because of the high sensitivity of this cluster ion to moisture and air, however, serious problems occurred.…”

Section: Mass Spectrometry and Quantum Chemical Calculationsmentioning

confidence: 99%

“…We therefore constructed a new ESI source which could be conditioned before the experiment in order to avoid contamination (especially by H 2 O). In the following paragraph, both experiments performed with the help of the new ESI source are described.ww 3.1 Mass spectrometric investigations of the dissociation of [C@W 6 Cl 17 ] À anions 22 In the experiments described here, the cluster anion [C@W 6 Cl 17 ] À , 1, is investigated in the gas phase after electrospray ionization (ESI) of a methanolic solution of Li 2 C@W 6 Cl 18 (which has been fully characterized by X-ray diffraction 36,37 ). By loss of Cl À from the dianion C@W 6 Cl 18 2À , 1 is formed.…”

Section: Mass Spectrometry and Quantum Chemical Calculationsmentioning

confidence: 99%

“…Afterwards, the degradation of 1 was observed step-by-step in collisionally activated dissociation (CAD) experiments. 22 In order to examine the stepwise fragmentation of this cluster species in the gas phase, several mass selection and dissociation experiments were performed. First, the most intense signal out of the great number of isotopomers of 1 could be identified at m/z = 1718.…”

Section: Mass Spectrometry and Quantum Chemical Calculationsmentioning

confidence: 99%

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Monitoring the dissolution process of metals in the gas phase: reactions of nanoscale Al and Ga metal atom clusters and their relationship to similar metalloid clusters

Burgert

Schnöckel

2008

Chem. Commun.

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Formation and dissolution of metals are two of the oldest technical chemical processes. On the atomic scale, these processes are based on the formation and cleavage of metal-metal bonds. During the past 15 years we have studied intensively the intermediates during the formation process of metals, i.e. the formation of compounds containing many metal-metal bonds between naked metal atoms in the center and ligand-bearing metal atoms at the surface. We have called the clusters metalloid or, more generally, elementoid clusters. Via a retrosynthetic route, the many different Al and Ga metalloid clusters which have been structurally characterized allow us to understand also the dissolution process; i.e. the cleavage of metal-metal (M-M) bonds. However, this process can be detected much more directly by the reaction of single metal atom clusters in the gas phase under high vacuum conditions. A suitable tool to monitor the dissolution process of a metal cluster in the gas phase is FT-ICR (Fourier transform ion cyclotron resonance) mass spectrometry. Snapshots during these cleavage processes are possible because only every 1-10 s is there a contact between a cluster molecule and an oxidizing molecule (e.g. Cl2). This period is long, i.e. the formation of the primary product (a smaller metal atom cluster) is finished before the next collision happens. We have studied three different types of reaction:(1) Step-by-step fragmentation of a structurally known metalloid cluster allows us to understand the bonding principle of these clusters because in every step only the weakest bond is broken.(2) There are three oxidation reactions of an Al13(-) cluster molecule with Cl2, HCl and O2 central to this review. These three reactions represent three different reaction types, (a) an exothermic reaction (Cl2), (b) an endothermic reaction (HCl), and (c) a kinetically limited reaction based on spin conservation rules (O2).(3) Finally, we present the reaction of a metalloid cluster with Cl2 in order to show that in this cluster only the central naked metal atoms are oxidized, and a smaller metalloid cluster results containing the entire protecting shell as the primary cluster. All the experimental results, supported by quantum chemical calculations, give a rough idea about the complex reaction cascades which occur during the dissolution and formation of metals. Furthermore, these results cast a critical light on many simplifying and generalizing rules in order to understand the bonding and structure of metal clusters. Finally, the experiments and some recent results provided by physical measurements on a crystalline Ga(84) compound build a bridge to nanoscience; i.e. they may be a challenge for chemistry in the next decades, since it has been shown that only with a perfect orientation of nanoscale metal clusters, e.g. in a crystal, can novel, unexpected properties (e.g. superconducting nanoscale materials) be obtained.

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Current literature in mass spectrometry

2005

J. Mass Spectrom.

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In order to keep subscribers up‐to‐date with the latest developments in their field, John Wiley & Sons are providing a current awareness service in each issue of the journal. The bibliography contains newly published material in the field of mass spectrometry. Each bibliography is divided into 11 sections: 1 Books, Reviews & Symposia; 2 Instrumental Techniques & Methods; 3 Gas Phase Ion Chemistry; 4 Biology/Biochemistry: Amino Acids, Peptides & Proteins; Carbohydrates; Lipids; Nucleic Acids; 5 Pharmacology/Toxicology; 6 Natural Products; 7 Analysis of Organic Compounds; 8 Analysis of Inorganics/Organometallics; 9 Surface Analysis; 10 Environmental Analysis; 11 Elemental Analysis. Within each section, articles are listed in alphabetical order with respect to author (4 Weeks journals ‐ Search completed at 8th. June 2005)

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Mass Spectrometric Investigations of the Dissociation of [C@W₆Cl₁₇]⁻ Ions in the Gas Phase

Cited by 10 publications

References 27 publications

Hexanuclear Niobium Cluster Compounds with Protonated N‐Base Cations

Hexanuclear Niobium Cluster Compounds with Protonated N‐Base Cations

Monitoring the dissolution process of metals in the gas phase: reactions of nanoscale Al and Ga metal atom clusters and their relationship to similar metalloid clusters

Current literature in mass spectrometry

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