Abstract

A method for the investigation of diastereoselective effects in reactions of gaseous ions bearing flexible backbones is described. It relies on the study of diastereoselectively labeled substrates that are studied by contemporary mass spectrometric means. While most examples discussed here deal with bond activations mediated by bare transition-metal ions in the gas phase, it is shown that the method is not restricted to this particular chemistry. Interestingly, the reason why transition-metal ions show relatively pronounced diastereoselective effects is that the activation barriers associated with their reactions are sufficiently small to be influenced by even subtle steric modifications of the substrate. Provided that suitable isotopically labeled precursors are investigated, even complex mechanistic schemes including competing side reactions can be analyzed by kinetic modeling of the isotope distributions in the reaction products.

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