Abstract
Four cationic manganese–tetracarbonyl complexes with the generic formula [Mn(CO)4(S2C·NHC)]PF6 that featured chelating imidazol(in)ium-2-dithiocarboxylate ligands derived from common N-heterocyclic carbenes bearing mesityl or 2,6-diisopropylphenyl substituents on their nitrogen atoms were readily synthesized by reacting the corresponding [MnBr(CO)3(S2C·NHC)] precursors with silver hexafluorophosphate in dichloromethane at room temperature in the presence or absence of added carbon monoxide. All the products were fully characterized by various analytical techniques and their most striking features on IR, NMR, and XRD spectroscopies were compared with those exhibited by related compounds. Their fragmentation in the gas phase was probed by using advanced mass spectrometry techniques. Upon CID, a clean decarbonylation of the parent [Mn(CO)4(S2C·NHC)]+ cations led to the formation of [Mn(CO)3(S2C·NHC)]+, [MnO2(S2C·NHC)]+, and [Mn(OH2)(S2C·NHC)]+ species.
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