ESI-FTICR-MS studies on gas phase fragmentation reactions of ArPd(PPh₃)₂I complexes

Abstract

Gas-phase fragmentation reactions of [ArPd(PPh 3 ) 2 ]ϩ were studied by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). The results of sustained off-resonance irradiation collision-activated dissociation (SORI-CAD) experiments provide detailed insights into mechanisms for the gas-phase fragmentation reactions of these complex ions. The POC bond cleavage mediated by palladium is investigated in the gas phase. There are two competitive fragmentation pathways for the complex ions [ArPd( ϩ (Ar ϭ p-OCH 3 -C 6 H 4 , p-CH 3 -C 6 H 4 , p-tBu-C 6 H 4 , p-NH 2 -C 6 H 4 , p-COCH 3 -C 6 H 4 , p-F-C 6 H 4 ), and the third pathway involves loss of one molecule of benzene and one PPh 3 ligand. The electronic effect and steric effect of the aryl groups also exhibit different influences on the fragmentation pathways. (J Am Soc Mass Spectrom 2006, 17, 1582-1589

Structural analysis of organometallic compounds with soft ionization mass spectrometry

“…Nevertheless, high-resolution ESI mass spectra offer the possibility of elemental composition determination-as illustrated with organopalladium (Evans et al, 2002) and organoplatinum compounds (Hartnell & Arnold, 2004). An appropriate mass analyzer can be useful to suggest a fragmentation mechanism as for ESI-FTICR-MS measurements of organopalladium ions with deuteriumlabeling experiments (Qian et al, 2006). Concerning other ionization techniques, the solution aggregation of the dinuclear palladium(I) complex was observed in FAB mass spectra, and, together with ESI spectra, confirmed the stability of polynuclear aggregates (Macchioni et al, 2003).…”

Analysis of the Volatile Compounds in Senecio Scandens Buch-Ham by Gas Chromatography—Tandem Mass Spectrometry Based on Diversified Scan Technologies

“…the isomers with special fragment ions were easily identified by the precursor ion scan and neutral loss scan technologies. [15][16][17][18][19][20][21][22] Here, a sensitive and specific gas chromatography(Gc)-MS/MS method combining the entire scan technologies of MS/MS was developed and validated. this method was used for the separation and qualitative Analysis of the volatile compounds in Senecio scandens Buch-Ham by gas chromatography-tandem mass spectrometry based on diversified scan technologies Introduction analysis of the volatile compounds of Senecio scandens Buch-Ham (referred to as S. scandens in the remainder of this paper).…”

“…Some compounds could produce particular neutral loss fragment with a retro-Diels-Alder (rDA) reaction in the EI source. 11,22,23 So, the neutral loss scan would easily distinguish the two compounds when only one of them has a particular neutral loss fragment according to the structure and the fragmentation mechanism of mass spectrometry of the compounds. two isomers, e, 4-terpineol, and f, b-terpineol, were considered as the candidate compounds for chromatographic peak 39 (figure 9).…”

ESI‐FTICRMS Characterization of the Intermediates in Cycloisomerization of Trifluoromethyl‐substituted Enynols through Changing the Protecting Group of Substrate

“…18,20,21 Though certain analogies between observations in the electrosprayed gas-phase intermediates and their existence in the solution-phase have been known for a long time, sometimes it is possible to establish organic reaction mechanism by extrapolating the findings from gas-phase chemistry to solution-phase chemistry. [21][22][23][24][25] In the previous work, we have used electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) to study the mechanism of some palladium-catalyzed organic reactions, and have successfully characterized some key intermediates of the reactions, [26][27][28][29] which provided some evidence to confirm the proposed mechanism.…”