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.