Reactions of permanganyl chloride with allene in low-temperature matrices

The light-induced (546 nm) reaction of MnO3Cl 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(OCCH2CH2) (1), and (O)2MnCl(H2COCCH2) (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.

Graphical abstractThe light-induced reaction of MnO3Cl with allene in low-temperature argon matrices at 11 K leads to the products (O)2MnCl(OCCH2CH2) (1), and (O)2MnCl(H2COCCH2) (2). DFT studies revealed that 2 can be formed on the singlet surface via attack at the central or terminal carbon atoms, while a spin-crossover proceeds the formation of 1.Figure optionsDownload full-size imageDownload as PowerPoint slide