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Electrospray ionization study of tricarbonyl fac ‐[Re(CO) 3 (PO)(X)]‐type complexes: influence of ancillary co‐ligands in the release of carbon monoxide
Author(s) -
Tisato Francesco,
Porchia Marina,
Shegani Antoni,
Maina Theodosia,
Papadopoulos Minas S.,
Seraglia Roberta,
Traldi Pietro
Publication year - 2018
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.8162
Subject(s) - chemistry , phosphine , electrospray ionization , denticity , fragmentation (computing) , medicinal chemistry , ligand (biochemistry) , carbon monoxide , mass spectrometry , pyridine , dissociation (chemistry) , tandem mass spectrometry , protonation , imidazole , inorganic chemistry , stereochemistry , crystallography , ion , organic chemistry , crystal structure , catalysis , chromatography , biochemistry , operating system , receptor , computer science
Rationale fac ‐[Re(CO) 3 (PO)(X)]‐type complexes (PO = chelated bidentate tertiary phosphine (1‐), X = various neutral, mono‐dentate ligands) represent a class of compounds that meets the synthetic criteria for the preparation of potential carbon monoxide (CO) release molecules (CORMs) for medicinal application. The aim of our investigation was to achieve qualitative information whether the nature of the ancillary X ligand might influence the release of CO. Methods The release of CO has been investigated by means of product ion spectrometry of electrospray ionization (ESI)‐generated [M + H] + species, produced by multiple collisional experiments, using an ion trap mass spectrometer. Results Tandem mass spectrometry applied to the protonated species [Re(CO) 3 (PO)(X) + H] + of seven complexes (those including X = OH 2 ( 1 ), isonitrile ( 2 , 3 ), imidazole ( 4 ), pyridine ( 5 ) and phosphine ( 6 , 7 )) shows initial loss of coordinated water ( 1 ) or pyridine ( 5 ), whereas the majority of investigated entries display initial, sequential release of CO groups. The energetics of CO release have been investigated by breakdown curves for selected collisionally activated decomposition processes involving CO, and compared with those involving X groups. Conclusions The nature of the co‐ligand X drives the primary loss in the MS n processes of [Re(CO) 3 (PO)(X) + H] + compounds. When X = solvent, the energetics of these decompositions follow the trend H 2 O < MeOH < CO. In each case, loss of CO is a favored fragmentation route with associated energies following the trend: N‐py ≤ P‐phosphine < C‐isonitrile. Overall, MS n pathways indicate that [Re(PO)] (Re with chelated PO phosphine) constitutes the residual moiety. This behavior indicates that the presence of a functionalized phosphine is essential for a sequential, controlled release of CO.

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