Gas Phase Protolysis of Trisarylzincate Anions.

Abstract

We have applied a combination of tandem-mass spectrometry, quantum-chemical calculations, and statistical rate theory computations to examine the gas phase reactions between the trisarylzincate anions ArXZnPh2- (ArX = p-X-C6H4, X = NMe2, OMe, Me, H, F, and Cl) and 2,2,2-trifluoroethanol at T = 310 ± 20 K. The observed reactions bring about the protonation of one of the aryl anions, which is then released as the corresponding arene, while the formed alkoxide binds to the zinc center. The protonation is faster for the more electron-rich aryl groups and shows a linear Hammett plot if the rate constant for X = NMe2 is discarded from the analysis. Although the reactions are highly exothermic, they proceed only with relatively low efficiencies (0.1% ≤ φ ≤ 1.3%). According to the quantum-chemical calculations, this behavior can be ascribed to the reactions proceeding through a double-well potential with a tight transition structure located at the central barrier. Based on these potential energy surfaces, the statistical rate theory computations can reproduce the measured rate constants within factors of 2 to 8. A comparison of the protolysis of the trisarylzincates with that of the corresponding free aryl anions demonstrates how the coordination to the metal center not only stabilizes the carbanions energetically but also moderates their reactivity. Thus, our gas phase study contributes to a better understanding of the fundamentals of organometallic reactivity.