New Approach to Substrate Activation or How Heterobimetallic Complexes {[(p-tBu-C6H4)2CH]3M}K (M = Ca and Yb) Make Intermolecular Olefin Hydroamination and NH3 Cascade Hydroamination/Hydroaminomethylation Feasible

Here, we report the synthesis and structures of two thermally stable base-free heterobimetallic benzhydryl complexes {[(p-tBuC6H4)2CH]3M}K (M = Yb(II) and Ca(II)) featuring the structures of contact ion pairs with the anionic part composed of three benzhydryl ligands η3-coordinated to the M(II) ion and K+ cation encapsulated by three η6-coordinated phenyl rings. The complexes demonstrated unprecedented catalytic activity and 100% regioselectivity in intermolecular olefin hydroamination allowing to involve into the reaction a broad scope of substrates including ethylene (1 atm), internal C═C bonds, and a variety of primary and secondary amines. Complex 1Ca allowed for the cascade NH3 alkylation with styrene and hydroaminoalkylation involving one of styryl fragments to afford N,N-diphenethyl-1,4-diphenylbutan-2-amine.