Probing Intermediates of Ion/Molecule Reactions by their Independent Gas‐Phase Synthesis and Fragmentation – The Thiomethoxymethyl Complexes [(bipy)M(CH₂SCH₃)]⁺ (M=Pt, Pd, Ni)

In the ion/molecule reaction (IMR) of “rollover”-cyclometalated [(bipy−H)Pt]+ with (CH3)2S, loss C2H4 from encounter complex was observed as main process some years ago. The cationic [(bipy)Pt(CH2SCH3)]+ identified a crucial intermediate by DFT calculations. order to prove its key role experimentally, cation has now been generated independently and studied collision-induced dissociation (CID). is loss, which proves be an also in IMR (CH3)2S. Based on calculations, thiomethoxymethyl complexes [(bipy)M(CH2SCH3)]+ (M=Pd Ni) would serve intermediates IMRs [(bipy−H)M]+. While these cannot explicitly, because parent ions generated, potential subjected CID. fragmentation channels for both metals corresponds loss. CID experiments thus provide insights into hypothetical [(bipy−H)M]+ comparison calculations all three Ni, Pd, Pt experimental findings uncovers subtle aspects underlying mechanisms. This work highlights suitability elucidation mechanisms well limitations this approach.