Shuttle HAT for mild alkene transfer hydrofunctionalization.

Hydrogen atom transfer (HAT) from a metal-hydride is a reliable and powerful method for functionalizing unsaturated C-C bonds in organic synthesis. Cobalt hydrides (Co-H) have garnered significant attention in this field, where the weak Co-H bonds are most commonly generated in a catalytic fashion through a mixture of stoichiometric amounts of peroxide oxidant and silane reductant. Here we show that the reverse process of HAT to an alkene, i.

Enhancing the Reactivity of an Aromatic cyclo-P Ligand via Electrophilic Activation.

Electrophilic activation of the aromatic cyclo-P ligand in [Cp*Fe(η-P)] is demonstrated to drastically enhance its reactivity towards weak nucleophiles. Unprecedented functionalized, contracted as well as complexly aggregated polyphosphorus compounds are accessed utilizing [Cp*Fe(η-PMe)][OTf] (A), highlighting the great potential of this underexplored mode of reactivity. Addition of carbenes to A affords novel 1,2- or 1,1-difunctionalized cyclo-P complexes [Cp*Fe(η-P(1-L)(2-Me)][OTf] (L=IDipp (1), CAAC (2), IPr (3 b)) and [Cp*Fe(η-P(1-IPr)(1-Me)][OTf] (3 a).