Reactions of permanganyl chloride with allene in low-temperature matrices

Abstract

The light-induced (546 nm) reaction of MnO 3Cl with allene has been investigated in low-temperature argon matrices at 11 K. IR spectroscopic studies in combination with isotopic enrichment experiments ( 18O, D) and DFT calculations (B3LYP/LanL2DZ) allowed the identification of (O ) 2MnCl(O CCH 2CH 2) ( 1), and (O ) 2MnCl(H 2COCCH 2) ( 2) as the products. Possible ways for their formation are first of all discussed qualitatively in the context of the literature available, and then quantitatively with the background of DFT data (B3LYP/6-311G(d)) obtained for starting materials, products, transition states and intermediates. The most reasonable interpretation involves two-state reactivity.