Radical-like reactivity for dihydrogen activation by coinage metal–aluminyl complexes: computational evidence inspired by experimental main group chemistry

The computational study of an unprecedented reactivity of coinage metal–aluminyl complexes with dihydrogen is reported. In close resemblance to group 14 dimetallenes and dimetallynes, the complexes are predicted to activate H 2 under mild conditions. Two different reaction pathways are found disclosing a common driving force, i.e., the nucleophilic behavior of the electron-sharing M–Al (M = Cu, Ag, Au) bond, which enables a cooperative and diradical-like mechanism. This mode of chemical reactivity emerges as a new paradigm for dihydrogen activation and calls for experimental feedback.