Handling considerations for the mass spectrometry of reactive organometallic compounds

Joshi, Anuj; Killeen, Charles; Thiessen, Tanner; Zijlstra, Harmen S.; McIndoe, J. Scott

doi:10.1002/jms.4807

Cited by 13 publications

(14 citation statements)

References 90 publications

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“…Nanoclusters produced by various synthetic methods are among the many types of analytes that are routinely studied by ESI-MS. , In addition, the ESI process itself can produce clusters. − For example, ESI of aqueous solutions containing certain X + cations can generate X + (H 2 O) n species, with prevalent n = 20 MNCs. ,, Similarly, electrosprayed amino acids form clusters, including the widely studied serine octamer MNC. − …”

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confidence: 99%

“…36,37 Thus, the properties of nascent analyte ions (immediately after release from the droplet) may differ from those of mature ions after in-source activation. 36,37 Only the latter are observable by MS. Nanoclusters produced by various synthetic methods are among the many types of analytes that are routinely studied by ESI-MS. 38,39 In addition, the ESI process itself can produce clusters. 40−42 For example, ESI of aqueous solutions containing certain X + cations can generate X + (H 2 O) n species, with prevalent n = 20 MNCs.…”

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confidence: 99%

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Mechanism of Magic Number NaCl Cluster Formation from Electrosprayed Water Nanodroplets

Konermann

Haidar

2022

Anal. Chem.

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Events taking place during electrospray ionization (ESI) can trigger the self-assembly of various nanoclusters. These products are often dominated by magic number clusters (MNCs) that have highly symmetrical structures. The literature rationalizes the dominance of MNCs by noting their high stability. However, this argument is not necessarily adequate because thermodynamics cannot predict the outcome of kinetically controlled reactions. Thus, the mechanisms responsible for MNC dominance remain poorly understood. Molecular dynamics (MD) simulations can provide atomistic insights into self-assembly reactions, but even this approach has thus far failed to provide pertinent answers. The current work overcomes this limitation. We focused on salt clusters formed from aqueous NaCl solutions during ESI. The corresponding mass spectra are dominated by the Na 14 Cl 13 + MNC. Simulations of ESI droplets showed nonspecific association of Na + and Cl − , culminating in gaseous clusters via solvent evaporation to dryness (charged residue mechanism). These nascent clusters did not show any preference for MNCs. In mass spectrometry experiments, analyte ions undergo in-source activation prior to detection. We emulated in-source activation by heating nascent clusters in our MD runs. Heating triggered structural fluctuations and dissociation events, generating MNC-dominated product distributions. Why are MNCs preferred after in-source activation? Thermally excited clusters frequently adopt structures consisting of a preformed MNC and a stringlike protrusion that contains the surplus ions. Facile separation of these protrusions releases the MNC (Cluster hot → MNC-protrusion → MNC + protrusion). This work marks the first time that MD simulations were able to capture cluster self-assembly with subsequent "molecular pruning", generating MNC-dominated product distributions that agree with experiments.

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Mechanism of Magic Number NaCl Cluster Formation from Electrosprayed Water Nanodroplets

Konermann

Haidar

2022

Anal. Chem.

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“…The structures and influence of the heterocumulenes and other viscosity modifiers with magnesium alkyls remained unexplored. Only little data on the structural elucidation of highly reactive water and air sensitive organometallic compounds are available, e.g., by using mass spectrometry for methyl aluminoxanes [ 33 , 34 ].…”

Section: Introductionmentioning

confidence: 99%

Structural Characterization of BIAN Type Molecules Used in Viscosity Reduction of Alkyl Magnesium Solutions

et al. 2023

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N1,N2-diphenylacenaphthylene-1,2-diimines (BIANs) have been used to reduce the undesired high viscosity of alkyl magnesium solutions, which are known to form polymeric structures. In order to understand the mechanisms, analyses of the BIAN alkyl magnesium solutions have been carried out under inert conditions with SEC-MS, NMR, and FTIR and were compared to the structures obtained from HPLC-MS, FTIR, and NMR after aqueous workup. While viscosity reduction was shown for all BIAN derivatives used, only the bis (diisopropyl)-substituted BIAN could be clearly assigned to a single reaction product, which also could be reused without loss of efficiency or decomposition. All other derivatives have been shown to behave differently, even under inert conditions, and decompose upon contact with acidic solvents. While the chemical reactions observed after the workup of the used BIANs are dominated by (multiple) alkylation, mainly on the C = N double bond, the observation of viscosity reduction cannot be assigned to this reaction alone, but to the interaction of the nitrogen atoms of BIANs with the Mg of the alkyl magnesium polymers, as could be shown by FTIR and NMR measurements under inert conditions.

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“…[17][18][19][20][21] One of the reasons for this is the extreme susceptibility of heavier tetrelylidyne complexes towards moisture and oxygen (with silicon usually the most sensitive due to its high oxophilicity), which impedes the sample introduction into the MS instrument. 22 As other analytical methods like IR or NMR greatly benefitted from advances in Schlenk and glove box techniques and became routinely applicable to sensitive samples, also mass spectrometry can rely on those methods to improve the handling of challenging compounds. Regarding the sample application, it is possible to install a glove box around the ionization source or inject the sample directly from a Schlenk tube.…”

Section: Introductionmentioning

confidence: 99%

“…17–21 One of the reasons for this is the extreme susceptibility of heavier tetrelylidyne complexes towards moisture and oxygen (with silicon usually the most sensitive due to its high oxophilicity), which impedes the sample introduction into the MS instrument. 22…”

Section: Introductionmentioning

confidence: 99%

Group 6 germylidyne complexes in the gas phase by LIFDI and APCI mass spectrometry

Maurer¹,

Engeser²

2022

Eur J Mass Spectrom (Chichester)

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Although showing fascinating chemical properties and reactivity in solution, heavier tetrelylidyne complexes with M≡E triple bonds have not been studied in the gas phase before due to their high sensitivity towards air and moisture. We selected four group 6 germylidyne complexes, [Cp(PMe3)2M≡GeArMes] (M = Mo (1-Mo), W (1-W), ArMes = 2,6-dimesitylphenyl) and [Tp’(CO)2M≡GeArMes] (M = Mo (2-Mo), W (2-W), Tp’ = κ3- N,N’,N’’-hydridotris(3,5-dimethylpyrazolyl) borate), for a mass-spectrometric study. Liquid Injection Field Desorption Ionization (LIFDI) proved to be a well-suited technique to ionize these sensitive compounds as the spectra show the molecular ions as radical cations and only minor traces of fragmentation or degradation products. In addition, Atmospheric Pressure Chemical Ionization (APCI) connected to a high-resolving tandem mass spectrometer allowed us to study the gas-phase fragmentation behaviour of these compounds. The fragmentation patterns not only comprise the expected losses of phosphane or carbonyl ligands, respectively, but also indicate C–H bond activation by the electron-deficient metal centre. An enhanced reactivity of the tungsten species is visible in a preferred methyl abstraction in the phosphane complex 1-W compared to 1-Mo. Although degradation in solution before ionization obviously can destroy the M≡Ge triple bond, the cleavage of the M≡Ge bond upon gas-phase activation is not observed for the Mo species and only as a minor pathway for the W compounds, highlighting the high bonding energy between metal and tetrel.

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Handling considerations for the mass spectrometry of reactive organometallic compounds

Cited by 13 publications

References 90 publications

Mechanism of Magic Number NaCl Cluster Formation from Electrosprayed Water Nanodroplets

Mechanism of Magic Number NaCl Cluster Formation from Electrosprayed Water Nanodroplets

Structural Characterization of BIAN Type Molecules Used in Viscosity Reduction of Alkyl Magnesium Solutions

Group 6 germylidyne complexes in the gas phase by LIFDI and APCI mass spectrometry

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