Gas-Phase Synthesis and Reactivity of Ligated Group 10 Ions in the Formal +1 Oxidation State

Electrospray ionization of the group 10 complexes [(phen)M(O₂CCH₃)₂] (phen=1,10-phenanthroline, M = Ni, Pd, Pt) generates the cations [(phen)M(O₂CCH₃)]⁺, 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). Decarboxylation of [(phen)M(O₂CCH₃)]⁺ under CID conditions generates the organometallic cations [(phen)M(CH₃)]⁺, which undergo bond homolysis upon a further stage of CID to generate the cations [(phen)M]^+· in which the metal center is formally in the +1 oxidation state. In the case of [(phen)Pt(CH₃)]⁺, the major product ion [(phen)H]⁺ was formed via loss of the metal carbene Pt=CH₂. DFT calculated energetics for the competition between bond homolysis and M=CH₂ loss are consistent with their experimentally observed branching ratios of 2% and 98% respectively. The IMR of [(phen)M]^+· with O₂, N₂, H₂O, acetone, and allyl iodide were examined. Adduct formation occurs for O₂, N₂, H₂O, and acetone. Upon CID, all adducts fragment to regenerate [(phen)M]^+·, except for [(phen)Pt(OC(CH₃)₂)]^+·, which loses a methyl radical to form [(phen)Pt(OCCH₃)]⁺ which upon a further stage of CID regenerates [(phen)Pt(CH₃)]⁺ via CO loss. This closes a formal catalytic cycle for the decomposition of acetone into CO and two methyl radicals with [(phen)Pt]^+· as catalyst. In the IMR of [(phen)M]^+· with allyl iodide, formation of [(phen)M(CH₂CHCH₂)]⁺ was observed for all three metals, whereas for M = Pt also [(phen)Pt(I)]⁺ and [(phen)Pt(I)₂(CH₂CHCH₂)]⁺ were observed. Finally, DFT calculated reaction energetics for all IMR reaction channels are consistent with the experimental observations.