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Characterisation via electrospray ionisation multistage mass spectrometry of three related series of nitrido technetium complexes containing phosphinothiolate and dithiocarbamate ligands
Author(s) -
Tubaro Michela,
Traldi Pietro,
Bolzati Cristina,
Tisato Francesco,
Refosco Fiorenzo,
Benini Elisa,
CavazzaCeccato Mario
Publication year - 2005
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.1998
Subject(s) - chemistry , dithiocarbamate , denticity , fragmentation (computing) , electrospray ionization , ligand (biochemistry) , moiety , protonation , molecule , mass spectrometry , medicinal chemistry , electrospray , metal , stereochemistry , ion , organic chemistry , chromatography , biochemistry , receptor , computer science , operating system
Abstract Nine nitrido technetium compounds comprising bis‐substituted Tc(N)(PS) 2 (1–4) (PS = bidentate phosphinothiolate ligands) and Tc(N)(dtc) 2 (5, 6) derivatives (dtc = bidentate dithiocarbamate), and mixed‐ligand Tc(N)(PS)(dtc) (7–9) species, were subjected to electrospray ionisation mass spectrometry and MS n experiments. Bis‐substituted phosphinothiolato complexes 1–4 lead to the straightforward formation of dinuclear species reasonably originating from proton bound dimers. These dinuclear species do not show, under collisionally induced fragmentation processes, the formation of monomeric units but cleavages related to the ligand framework, thereby proving the high stability of the [TcH + Tc] bond. Bis‐dithiocarbamate compounds 5 and 6 show, instead, abundant [M+H] + , [M+Na] + and [2M+Na] + ions, and their collisionally induced fragmentations are highly favoured with cleavages related to the CN and CS bonds. During these processes, the coordination of a water molecule to [MH–L] + product ions is observed, as proved by the collisionally induced H 2 O loss detected for this species. Mixed‐ligand compounds 7 and 8 show the protonated molecules and Na + ‐cationised ions with fragmentation processes related to the dithiocarbamate moiety. This behaviour indicates that coordination of ether‐ and ester‐substituted dithiocarbamates to the [Tc N] group is weaker than that of phosphinothiolates. Conversely, diethyldithiocarbamate inserted in mixed complex 9 enhances both CN and TcS bonds, and fragmentation processes suggest that metal‐phosphinothiolate and metal‐dithiocarbamate show comparable strength. Copyright © 2005 John Wiley & Sons, Ltd.