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Electrospray ionisation of the ligated group 10 metal complexes [(phen)M(O 2 CCH 3 ) 2 ] (M = Ni, Pd, Pt) generates the cations [(phen)M(O 2 CCH 3 )] + , whose gas-phase chemistry was studied using multistage mass spectrometry experiments in an ion trap mass spectrometer with the combination of collision-induced dissociation (CID) and ion-molecule reactions (IMR). A new catalytic cycle has been discovered. In step 1, decarboxylation of [(phen)M(O 2 CCH 3 )] +  under CID conditions generates the organometallic cations [(phen)M(CH 3 )] + , which react with acetone to generate the [(phen)M(CH 3 )(OC(CH 3 ) 2 )] +  adducts in competition with formation of the coordinated enolate for M = Pt (step 2). For M = Ni and Pd, the adducts regenerate [(phen)M(CH 3 )] +  upon CID. In the case of M = Pt, loss of methane is favored over loss of acetone and results in the formation of the enolate complex, [(phen)Pt(OC(CH 2 )CH 3 )] + . Upon further CID, both methane and CO loss can be observed resulting in the formation of the ketenyl and ethyl complexes [(phen)Pt(OCCH)] +  and [(phen)Pt(CH 2 CH 3 )] +  (step 3), respectively. In step 4, CID of [(phen)Pt(CH 2 CH 3 )] +  results in a beta-hydride elimination reaction to yield the hydride complex, [(phen)Pt(H)] + , which reacts with acetic acid to regenerate the acetate complex [(phen)Pt(O 2 CCH 3 )] +  and H 2  in step 5. Thus, the catalytic cycle is formally closed, which corresponds to the decomposition of acetone and acetic acid into methane, CO, CO 2 , ethene and H 2 . All except the last step of the catalytic cycle are modelled using DFT calculations with optimizations of structures at the M06/SDD 6-31G(d) level of theory.

zeitschrift für physikalische chemie

Gas-Phase Reactions of the Group 10 Organometallic Cations, [(phen)M(CH 3 )] +  with Acetone: Only Platinum Promotes a Catalytic Cycle via the Enolate [(phen)Pt(OC(CH 2 )CH 3 )] +