Frustrated Lewis pair‐catalyzed hydrogenation of unactivated alkenes with sterically hindered 9‐phosphatriptycenes

Abstract

The frustrated Lewis pair-catalyzed hydrogenation of unactivated alkenes with H 2 is reported. The weak Lewis basicity and high steric hindrance of ortho-substituted 9-phosphatriptycene derivatives is taken as an advantage to catalyze this reaction in combination with tris(pentafluorophenyl)borane. A scope of unsaturated substrates is described. The thermodynamics and kinetics of hydrogenation investigated by density functional theory show that the protonation of the olefin by the strongly acidic phosphonium cation is the critical step of the reaction.

Significantly enhanced catalytic performance of Pd nanocatalyst on AlOOH featuring abundant solid surface frustrated Lewis pair for improved hydrogen activation

“…[4][5][6] However, a novel and unconventional approach to hydrogen dissociation is attracting growing attention, incorporating the utilization of frustrated Lewis pair (FLP). 7,8 This represents a distinctive method of hydrogen dissociation and relies signicantly on the proximity distance between the Lewis acid and base sites. 9,10 Controlling the distance between the Lewis acid and base sites is easy in homogeneous catalysts, which is why most FLP hydrogen dissociation behaviors occur in homogeneous catalytic systems.…”

“…4–6 However, a novel and unconventional approach to hydrogen dissociation is attracting growing attention, incorporating the utilization of frustrated Lewis pair (FLP). 7,8 This represents a distinctive method of hydrogen dissociation and relies significantly on the proximity distance between the Lewis acid and base sites. 9,10…”

A Rigid Linker for Site-Selective Coordination of Transition Metal Cations: Combining an Acetylacetone with a Caged Phosphine

“…Recently we approached this issue by introducing the caged phosphine scaffold of the triptycene into CP chemistry . The triptycene scaffold not only gives a rigid linear linker, but it also stabilizes the phosphorus further, making it resistant toward oxidation with ambient oxygen in both solid state and solution. , Furthermore, the geometrical changes induced by the caged scaffold lower the basicity and increase the π-acidity of the phosphorus, strengthening its interaction with soft transition metal cations. − …”

Fusing Triphenylbismuth and PnPh3 (Pn = P–Bi): Synthesis, Isolation, and Characterization of 9-Bisma-10-Pnictatriptycenes

“…Among the (di)­pnictatriptycenes, especially phosphatriptycenes, phosphaboratatriptycenes, and phosphasilatriptycenes have been employed in the fields of transition-metal catalyzed C–C cross-coupling reactions − and ortho -selective CH borylation of N-functionalized arenes, , as ditopic linkers in supramolecular chemistry − and as Bro̷nsted bases in frustrated Lewis pair (FLP) chemistry. , Moreover, azaphosphatriptycenes have been utilized as molecular gears or as ligands in the hydroformylation of internal alkenes and enol ethers . Furthermore, a derivative of III–P/Bi , 2,3,6,7,14,15-hexamethyl-9-phospha-10-bismatriptycene, has been used for the preparation of nonstabilized phosphonium ylides and exploited in Wittig reactions …”