Electron ionization mass spectrometry in the characterization of azidonitriles

Martins, Filipa; Duarte, M. Filomena; Fernandez, M. Tereza; Langley, G. John; Rodrigues, Paula C.; Barros, M. Teresa; Costa, M.L.

doi:10.1002/rcm.1331

Cited by 7 publications

(3 citation statements)

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“…No ambiguity remains on the loss of 28 Da from 3-azidopropionitrile, which is attributable to loss of N 2 . In fact, previous studies on 3-azidopropionitrileá [22]áshowedáthatátheámolecularáion loses N 2 but not H 2 CN. In addition, there is agreement in the literature about the loss of N 2 as a first step of decompositionáofáorganicáazidesá[18á -20].áTheálossáofáHCl does not change the charge of the complex or the oxidation state of the metal as, apparently, a proton is donated by the ligand that becomes negatively charged.…”

Section: Ms-ms Analysismentioning

confidence: 98%

“…An important feature in the reactivity of organoazides is the loss of molecular nitrogen, which can be induced thermally, photochemically,áorácatalyticallyábyáacidáorátransitionámetalsá [18á -20].áInáspiteáofátheiráinstability,ásomeáspectroscopic studies have been performed to monitor their decompositioná [21][22][23][24][25].áSomeáofátheáaliphaticáazidesáspectro-scopically investigated, such as, azidoacetic acid, azidoacetone, and azidonitriles, have been selected for studies of their decomposition on surfaces. So far, azidoacetic acid is the only aliphatic azide for which a surface study of its decomposition has been completed [26];ápreviously,áhydrazoicáacidáhadábeenáinvestigated asáaáprecursoráinásemiconductorápreparationá [27][28][29].…”

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Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Couto

Duarte

Fernandez

et al. 2007

J. Am. Soc. Mass Spectrom.

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Most complexes of azides and transition metals involve the N 3Ϫ azide anion as a ligand other than an organic azide. Complexes of organic azides with metals are involved in biological applications and in the deposition of nitrenes on metal surfaces, producing nitride layers for semi-conductors preparation; this makes the study of these interactions an important issue. This work describes a study of the complexation of nickel and cobalt by 3-azidopropionitrile by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of NiCl 2 and CoCl 2 in methanol/water. In the case of nickel, other NiX 2 salts were investigated (where X ϭ Br or NO 3 ) and other solvents were also studied (notably ethanol/water). All complexes detected were single positively charged, with various stoichiometries, some resulted from the fragmentation of the ligand, the loss of N 2 , and HCN being quite common. The most abundant cations observed were [Ni(II)AzAzX] ϩ , where X ϭ Cl, Br, NO 3 . Some of the complexes showed solvation with methanol/ethanol/water. Metal reduction was observed in complexes where a radical was lost, resulting from the homolytic cleavage of a metalOnitrogen bond. Collision induced dissociation (CID) experiments followed by tandem mass spectrometry (MS-MS) analysis were not absolutely conclusive about the coordination site. However, terminal ions observed from the fragmentation routes were explained by a proposed gas-phase mechanism. Density functional theory calculations were carried out and provided structures for some complexes, pointing to the possibility of 3-azidopropionitrile acting as a mono-or a bidentate ligand. (J Am Soc Mass Spectrom 2007, 18, 453-465)

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Section: Ms-ms Analysismentioning

confidence: 98%

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confidence: 99%

Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Couto

Duarte

Fernandez

et al. 2007

J. Am. Soc. Mass Spectrom.

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“…Some of us have applied different approaches to investigate some aliphatic azides. Azidoacetic acid, azidoacetone and azidonitriles were spectroscopically investigated,20, 26–28 and were also selected for studies of their decomposition on surfaces. Formerly, hydrazoic acid had been investigated as a precursor in semiconductor preparation 29–31.…”

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Study of doubly charged alkaline earth metal and 3‐azidopropionitrile complexes by electrospray ionization mass spectrometry

Couto

Ramos

Fernandez

et al. 2008

Rapid Comm Mass Spectrometry

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The present work describes a study of the complexation of calcium and magnesium by 3-azidopropionitrile by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of calcium and magnesium salts of the type CaX2 and MgX2 (where X = Cl or NO3) in water and methanol/water. The complexes detected were mainly double positively charged, with various stoichiometries not depending on the solvent, since water and 3-azidopropionitrile were always the main ligands. Solvation with methanol was not observed unlike in a previous study of complexation of nickel and cobalt by 3-azidopropionitrile. The complex ions [M(II)Az4(H2O)](2+), [M(II)Az5](2+) (where M = Ca and Mg) are the most abundant for both metals, and both counter ions. Tandem mass spectrometric (MS/MS) analysis showed that, under collision-induced dissociation (CID) conditions, the most important processes occurring were loss of neutral ligands and the replacement of 3-azidopropionitrile by water. A complex species containing reduced alkaline earth metal was due to radical loss, resulting from homolytic cleavage in the azide ligand. Some terminal ions, in the fragmentation sequences, point to the nitrile group as the coordination site in the 3-azidopropionitrile. Density functional theory (DFT) calculations confirmed this coordination site and proved that 3-azidopropionitrile behaves as a monodentate ligand in the systems under study. Moreover, the theoretical study proved that the presence of water ligand introduces stability through a hydrogen bond established between the water molecule and one nitrogen atom of the azido group. In addition, the strong dipole moment of 3-azidopropionitrile (4.76 D), which is mainly related to presence of the nitrile group, favors the stabilization of the metal-ligand complexes through charge-dipole interactions and the coordination of the metal to the nitrile group.

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Sodium Azide

Turnbull

Narsaiah

Yadav

et al. 2008

Encyclopedia of Reagents for Organic Synthesis

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Electron ionization mass spectrometry in the characterization of azidonitriles

Abstract: Scheme 6. Mechanism proposed for loss of HN 2. radical from molecular ion of compound 3.Scheme 7. Mechanism proposed for the formation of the fragment ion at m/z 40 from the fragment ion at m/z 68 from compound 2.366 Letter to the Editor

Cited by 7 publications

References 7 publications

Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Study of doubly charged alkaline earth metal and 3‐azidopropionitrile complexes by electrospray ionization mass spectrometry

Sodium Azide

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