Mass Spectrometry of Inorganic, Coordination and Organometallic Compounds

Henderson, William; McIndoe, J. Scott

doi:10.1002/0470014318

Cited by 243 publications

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“…T he experimental study of the structure and reactivity of gas-phase organometallic species by mass spectrometry (MS) has aroused a great interest with the advent of new mass analyzers and new ionization sources, especially those operating from the condensed phase [1][2][3]. Electrospray ionization (ESI) occupies a central position in the strategy for establishing a connection between the metal-containing ions existing in solution and those observed in the gas phase.…”

Section: Introductionmentioning

confidence: 99%

A Quantitative Approach of the Interaction between Metal Triflates and Organic Ligands Using Electrospray Mass Spectrometry

Gal

Iacobucci

Monfardini

et al. 2012

J. Am. Soc. Mass Spectrom.

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The interaction between two Lewis "superacid" catalysts Zn(OTf) 2 and In(OTf) 3 and series of amide and phosphate ligands is quantitatively characterized by electrospray ionization mass spectrometry (ESI-MS). A specific feature of the ESI-MS spectra of the mixture of metal triflates and Lewis bases is the formation of ionic adducts resulting from the displacement of one triflate anion by two neutral ligands. A ligand competition model is developed, which describes the relative intensities of the ionic adducts as a function of relative ligand concentrations. The relative affinities deduced from the ligand competition method are combined in an affinity scale for the metal triflate.

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Section: Introductionmentioning

confidence: 99%

A Quantitative Approach of the Interaction between Metal Triflates and Organic Ligands Using Electrospray Mass Spectrometry

Gal

Iacobucci

Monfardini

et al. 2012

J. Am. Soc. Mass Spectrom.

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“…27 GC analyses were performed either on a Hewlett-Packard HP 5890 Series II gas chromatograph X-ray structure analysis of crystals 4, 5 and 9: Crystals were grown by slow diffusion of hexane into dichloromethane solutions. In all cases, the crystals were coated with perfluoropolyether, mounted on a glass fiber and fixed in a cold nitrogen stream (T = 100(2) K) to the goinometer head.…”

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confidence: 99%

Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

et al. 2014

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The reaction between pyridine and [8, (17, 18, 19). These series of  2 -C 2 H 4 -and CO-ligated 11-vertex isonido / closorhodathiaboranes result from the substitution of one PPh 3 ligand by ethylene or CO together with H 2 loss and a concomitant nido-to-closo / isonido-cluster structural transformation. The reactivity of 3-5 with propene, 1-hexene and cyclohexene in a hydrogen atmosphere is also reported and compared with the reactivity of the pyridine-ligated analogue, [8,8,8-(H)(PPh 3 ) 2 -9-(NC 5 H 5 )-nido-8,7-RhSB 9 H 9 ] (2). Low temperature NMR studies have allowed the characterization of intermediates which undergo inter-and intramolecular exchange processes, depending on the nature of the N-heterocyclic ligand. The CO ligand enhances the non-rigidity of the cluster, opening mechanisms of H 2 loss from the clusters.) 3MANUSCRIPT TEXT

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“…Of course, the valency of the metal cation and the anion must be different; otherwise the complex would not be charged and would not be observed in the ESI mass spectra. As counter ions, we decided to use the three Cl [11]. One of the metal reduction mechanisms upon the ESI condition is the loss of a respective radical (applying a higher cone voltage, which leads to the so-called in-source fragmentation) from the counter ion containing species, e.g., [12,13].…”

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confidence: 99%

Anion-π interactions—interactions between benzo-crown ether metal cation complexes and counter ions

Frański

Gierczyk

Schroeder

2009

J. Am. Soc. Mass Spectrom.

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The loss of X · radical from [M ϩ Cu ϩ X] ϩ ions (copper reduction) has been studied by the so called in-source fragmentation at higher cone voltage (M ϭ crown ether molecule, X Ϫ ϭ counter ion, ClO 4 Ϫ , NO 3 Ϫ , Cl Ϫ ). The loss of X · has been found to be affected by the presence/lack of aromatic ring poor/rich in electrons. Namely, the loss of X · occurs with lower efficiency for the [NO 2 -B15C5 ϩ Cu ϩ X] ϩ ions than for the [B15C5 ϩ Cu ϩ X] ϩ ions, where NO 2 -B15C5 ϭ 3-nitro-benzo-15-crown-5, B15C5 ϭ benzo-15-crown-5. A reasonable explanation is that Anion-interactions prevent the loss of X · from the [NO 2 -B15C5 ϩ Cu ϩ X] ϩ ions. The presence of the electron-withdrawing NO 2 group causes the aromatic ring to be poor in electrons and thus its enhances its interactions with anions. For the ion containing the aromatic ring enriched in electrons, namely [NH 2 -B15C5 ϩ Cu ϩ ClO 4 ] ϩ where NH 2 -B15C5 ϭ 3-amino-benzo-15-crown-5, the opposite situation has been observed. Because of Anionrepulsion the loss of X · radical proceeds more readily for [ϩ . Iron reduction has also been found to be affected by Anion-interactions. Namely, the loss of . Among others, the authors discussed in details arene-arene interactions, hydrogen bonding to aromatic systems, cationinteractions, and the influence of counter ions on the cation-interactions. The possibility that aromatic ring may also interact with the anion due to the Anioninteractions has not been mentioned, which indicates that the anion-interactions are not so common. Indeed, the chemistry of noncovalent Anion-interactions is much less developed than that of the other types of interactions. Most likely the reason is the electrondonating character of anions, which is expected to lead to repulsive interactions with aromatic clouds. Anioninteractions are energetically less favorable than their cation-counterparts because the anions have greater van der Waals radii than cations and the binding energies strongly depend upon distance [2][3][4][5][6].In the field of supramolecular chemistry, crown ethers (CE) belong to the most popular hosts since their inclusion complexes have found a vast number of practical applications [7]. The aromatic ring-containing crown ethers may have enhanced complexing properties due to the -stacking interactions. It has been found that cation-interactions are of crucial importance for formation of complexes between dibenzo-24-crown-8 and tetramethylammonium cation [8]. Donoracceptor -stacking interactions have been established to significantly enhance the formation of mixed-ligand sandwich complexes formed by crown ethers [9]. Crown ethers having aromatic sidearms exhibited cation-interactions between K ϩ and a benzene ring [10]. Here we asked if the complexes of benzo-crown ethers with metal cation interact with the anion through the anion-interactions and if this interaction can be observed by ESI-MS. Obviously, a benzo-crown ether should contain an aromatic ring poor in electrons, e.g., nitro-benzo-15-crown-5 (NO 2 -B15C5). To the best of...

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Mass Spectrometry of Inorganic, Coordination and Organometallic Compounds

Cited by 243 publications

References 0 publications

A Quantitative Approach of the Interaction between Metal Triflates and Organic Ligands Using Electrospray Mass Spectrometry

A Quantitative Approach of the Interaction between Metal Triflates and Organic Ligands Using Electrospray Mass Spectrometry

Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

Anion-π interactions—interactions between benzo-crown ether metal cation complexes and counter ions

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