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Unexpected formation of [M]2+from [M+CuCl+H]2+ions under CID conditions, where M is a molecule of 3,5-bis(2,2’-bipyridin-4-ylethynyl)benzoic acid or its methyl ester

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Frański R., Zalas M., Gierczyk B., Cegłowski M., Schroeder G., Kozik T., Hoffmann M.

Open Chemistry

2015

vol. 13

issue 1

[M+CuCl+H]2+ ions were generated using electrospray ionization (ESI); where M is a molecule of 3,5-bis(2,2’-bipyridin-4-ylethynyl)benzoic acid or its methyl ester (1 and 2, respectively). The ions were subjected to CID-MS/MS analysis. It was found that their gas phase decomposition lead to the formation of rare di-cations [M]2+, namely [1]2+ and [2]2+ ions. The formation of [1]2+ ion from [3+H+CuCl]2+ ion in the second fragmentation, where 3 is ethyl ester of 3,5-bis(2,2-bipyridin-4-ylethynyl)benzoic acid, was also observed since in the first fragmentation step the loss of ethylene molecule from [3+H+CuCl]2+ ion took place. To the best of our knowledge, it is the first time that [M]2+ ions formation from respective metal complexes has been reported. It is also unusual that formation of [M]2+ ions is not accompanied by formation of [M]+∙ ions. Furthermore, as expected, theoretical calculation and electron ionization mass spectra show that 1 and 2 are not especially prone to form [M]2+ ions. Thus formation of [M]2+ ions under CID conditions is very surprising.

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1 Open Chemistry

1 2015

1 Cegłowski M.

1 Frański R.

1 Gierczyk B.

1 Hoffmann M.

1 Kozik T.

1 Schroeder G.

1 Zalas M.

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Unexpected formation of [M]2+from [M+CuCl+H]2+ions under CID conditions, where M is a molecule of 3,5-bis(2,2’-bipyridin-4-ylethynyl)benzoic acid or its methyl ester