Role of the Metal, Ligand, and Alkyl/Aryl Group in the Hydrolysis Reactions of Group 10 Organometallic Cations [(L)M(R)]⁺

The reactions of water with the coordinatively unsaturated group 10 organometallic cations [(L)M(R)]+ (4; where L = 1,10-phenanthroline (phen), neocuproine (neo); M = nickel, palladium, platinum; R = CH3, C6H5, CH2C6H5), formed via decarboxylation of the carboxylate complexes [(L)M(O2CR)]+, were examined in the gas phase using a combination of multistage mass spectrometry experiments and DFT calculations at the M06/SDD6-31+G(d) level of theory. Two main types of primary product ions were observed: the aqua adduct [(L)M(R)(H2O)]+ (5) and the hydroxide [(L)M(OH)]+ (7), formed via a hydrolysis reaction. A secondary product ion, arising from formation of the adduct [(L)M(OH)(H2O)]+, was also observed when L = phen, R = CH3, and M = Pt. The rates of reaction of 4 and the product branching ratios for 5 and 7 were dependent upon the nature of M, L, and R. When L = phen and R = CH3, the hydroxide 7 dominates for Ni, with the adduct 5 as the major product for both Pd and Pt. For R = C6H5 the rate of the reaction i...