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 is slower, while for R = CH₂C₆H₅ no reaction occurs. Replacing the phen auxiliary ligand with neo dramatically slows down the rate of reaction with water. DFT calculations reveal that an acid−base hydrolysis mechanism is favored over an oxidative addition/reductive elimination mechanism proceeding via the M(IV) intermediate [(L)M(CH₃)(H)- (OH)]⁺. Furthermore, the relative energies calculated for the barriers of these hydrolysis reactions are consistent with the experimentally observed reactivity trends. This mechanism is also supported by RRKM theory/master equation simulations, which demonstrate that formation of the aqua adduct and hydroxide can be explained by competition between unimolecular dissociation and collisional deactivation of the chemically activated reaction adduct within the ion trap. The lack of reactivity of the benzyl systems appears to arise from η³ binding of the benzyl group, which blocks access to the incoming water. Finally, links are made to group 10 three-coordinate organometallic complexes in the condensed phase.

Item Type:	Refereed Article
Keywords:	organometallic
Research Division:	Chemical Sciences
Research Group:	Inorganic Chemistry
Research Field:	Transition Metal Chemistry
Objective Division:	Manufacturing
Objective Group:	Industrial Chemicals and Related Products
Objective Field:	Organic Industrial Chemicals (excl. Resins, Rubber and Plastics)
Author:	Yates, BF (Professor Brian Yates)
ID Code:	89215
Year Published:	2013
Web of Science® Times Cited:	16
Deposited By:	Chemistry
Deposited On:	2014-02-26
Last Modified:	2017-10-25
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