TY - JOUR
T1 - Gas-phase interaction between nickel (II) and nitrobenzyl azides: an ESIMS study
AU - Cunha, Bárbara M. P.
AU - Trindade, Inês N.
AU - Couto, Narciso A. S.
AU - Costa, Paulo J.
AU - Costa, Maria de Lourdes Santos Lourenço
AU - Rodrigues, Paula Cristina Alves
AU - Barros, Maria Teresa
AU - Costa, Maria Lourdes S. L.
AU - Duarte, Maria Filomena N.
AU - Fernandez, M. Tereza
AU - Madeira, Paulo J. Amorim
N1 - Sem PDF conforme despacho.
The NMR spectrometer is part of The National NMR Network (REDE/1517/RMN/2005) and the Fourier Transform Ion Cyclotron Resonance Mass Spectrometer is part of the National Mass Spectrometry Network (REDE/1501/REM/2005), supported by "Programa Operacional Ciencia e Inovacao (POCI) 2010" and Fundacao para a Ciencia e a Tecnologia (FCT). This work has been supported by FCT through grant nos. PEst-OE/EQB/LA0004/2011, PEst-C/EQB/LA0006/2011 and Pest-OE/QUI/UI0612/2011. P.J.C. thanks FCT for the postdoctoral grant SFRH/BPD/27082/2006. P.J.A.M. thanks FCT for the postdoctoral grant SFRH/BPD/86948/2012. The authors thank Prof. M. Helena Garcia for the helpful discussions on coordination chemistry topics.
PY - 2013/10/1
Y1 - 2013/10/1
N2 - Organoazides are intermediates in the synthesis of imidometal complexes. Metalimido complexes have an important role in catalysis. Thus, the organoazide interaction with metals is an important issue. However, the isolation of organoazidometal complexes is difficult due to the easy loss of N2. The present study describes the complexation of nickel by nitrobenzyl azides by means of electrospray ionization mass spectrometry (ESI-MS), which was used also as a probe for the characterization of isomers. Organoazidometal complexes were observed and isolated from solutions of NiCl2and NiBr2in methanol/water. A different solvent, ethanol/water was also used. The complexes detected were singly and doubly positively charged, with various stoichiometries. The most abundant species were [Ni(II)Az3]2+forortho-andpara-isomers, and [Ni(II)Az3(H2O)]2+for meta isomer, where Az stands for nitrobenzyl azides. Theorthoisomer showed several single positively charged complexes integrating chloride as a ligand. The mass spectra of the three isomers allowed their differentiation based on different behaviour in the mass rangem/z296–m/z312. The MS2spectra of [Ni(II)Az3]2+were investigated aiming to characterize the three isomers but this analysis was not absolutely conclusive about the coordination site(s). Density functional theory calculations provided possible structures for the [Ni(II)Az3]2+cation with the different isomers and their coordination modes could be responsible for their fragmentation pathways
AB - Organoazides are intermediates in the synthesis of imidometal complexes. Metalimido complexes have an important role in catalysis. Thus, the organoazide interaction with metals is an important issue. However, the isolation of organoazidometal complexes is difficult due to the easy loss of N2. The present study describes the complexation of nickel by nitrobenzyl azides by means of electrospray ionization mass spectrometry (ESI-MS), which was used also as a probe for the characterization of isomers. Organoazidometal complexes were observed and isolated from solutions of NiCl2and NiBr2in methanol/water. A different solvent, ethanol/water was also used. The complexes detected were singly and doubly positively charged, with various stoichiometries. The most abundant species were [Ni(II)Az3]2+forortho-andpara-isomers, and [Ni(II)Az3(H2O)]2+for meta isomer, where Az stands for nitrobenzyl azides. Theorthoisomer showed several single positively charged complexes integrating chloride as a ligand. The mass spectra of the three isomers allowed their differentiation based on different behaviour in the mass rangem/z296–m/z312. The MS2spectra of [Ni(II)Az3]2+were investigated aiming to characterize the three isomers but this analysis was not absolutely conclusive about the coordination site(s). Density functional theory calculations provided possible structures for the [Ni(II)Az3]2+cation with the different isomers and their coordination modes could be responsible for their fragmentation pathways
KW - Isomer differentiation
KW - Electrospray ionization
KW - DFT calculations
KW - Nitrobenzyl azides’ complexes
KW - Tandem mass spectrometry
KW - DFT calculations
KW - Electrospray ionization
KW - Isomer differentiation
KW - Nitrobenzyl azides' complexes
KW - Tandem mass spectrometry
U2 - 10.1016/j.ijms.2013.05.012
DO - 10.1016/j.ijms.2013.05.012
M3 - Article
VL - 351
SP - 27
EP - 36
JO - International Journal of Mass Spectrometry
JF - International Journal of Mass Spectrometry
SN - 1387-3806
ER -