Phosphorus Lewis acids: emerging reactivity and applications in catalysis

Abstract

Part of the renaissance in main group chemistry has been a result of the focus on reactivity. This has led to the development of applications in stoichiometric reactivity and catalysis. In this tutorial review, we focus attention on the role of phosphorus-based Lewis acids in such advances. While early literature recognizes the role of P(iii) and P(v) electrophiles in coordination chemistry, it has generally been more recent studies that have focused on applications of this Lewis acidity. Applications of these novel P-based Lewis acids in stoichiometric reactivity, Lewis acid catalysis and frustrated Lewis pair (FLP) reactivity are reviewed. These advances demonstrate that P-based Lewis acids are a powerful tool for further developments in metal-free catalysis.

Fluorinated antimony(v) derivatives: strong Lewis acidic properties and application to the complexation of formaldehyde in aqueous solutions

“…Recent efforts have shown that electrophilic phosphorus( v ) compounds 13 can be used as Lewis acid catalysts for organic reactions 14–18 as well as in FLPs for hydrogenations 19 and CO 2 capture reactions. 20 Inspired by these advances and using fluoride anion affinity data as a guide, 21,22 several groups have paid a renewed attention to the properties of antimony( v ) compounds.…”

Supramolecular aggregation in dithia-arsoles: chlorides, cations and N-centred paddlewheels

“…21 In addition, we find 2 is polymorphic and compare the structures of 2α, initially reported by Kisenyi et al,22 with the new polymorph 2 in relation to 1 and other dithia-chloroarsoles. Treatment of 2 with the Lewis acids MCl3 (M = Al, Ga) affords the iso-morphous pair of dithia-arsolidinium cations [3] MCl4] (3a M = Al, 3b M = Ga) in which the cations are located on a crystallographic mirror plane. Addition of 2 to LiN SiMe3)2 in a 3 : 1 ratio leads to formation of the paddlewheel complex 4 (Scheme 1) which exhibits supramolecular aggregation through close S⋯S contacts.…”

S–H Bond Activation in Hydrogen Sulfide by NHC-Stabilized Silyliumylidene Ions

“…In earlier work by Müller and coworkers, they obtained the analogous species with the bulkier mTer iPr ligand by the reaction of the NHC-stabilized hydridosilylene with elemental sulfur [62]. BmTer iPr features the same 1 JSiH coupling constant (209 Hz), which is smaller compared to the one of silathioformamide (255 Hz) reported by Driess and coworkers. [50].…”

“…Low-valent main group chemistry is a rapidly developing field and the wealth of new structural motifs, which have been isolated in the past two decades, have increasingly gained interest in using these species for the activation of small molecules and, potentially, for catalysis (for representative reviews see [1][2][3][4][5][6][7]). Key to these developments have been the usage of suitable synthetic methodologies in combination with thermodynamic and kinetic stabilization by appropriately chosen ligands.…”