Geometrically Deformed and Conformationally Rigid Phosphorus Trisamides Featuring an Unsymmetrical Backbone.

Nonclassical P(III) centers have attracted much attention in recent years. Incorporating a P(III) center in a rigid bicyclic platform offers a particularly attractive way to invoke significant geometric distortion of the phosphorus atom that may in turn induce unusual reactivity. Although still relatively scarcely explored, phosphorus centers enforced in a non-C3 symmetry have gained significant traction lately. However, the current scaffolds are based on a relatively limited set of design principles and ligand platforms associated therewith. This work is focussed on the synthesis as well as versatile oxidation, addition and coordination chemistry of a geometrically distorted P(III) species featuring a synthetically modular, nonsymmetric trisamine platform derived from 2-(methylamino)-N-(2-(methylamino)phenyl)benzenesulfonamide. Incorporating a P(III) center in a rigid bicyclic platform offers an attractive way to invoke significant geometric distortion of the phosphorus atom. Current scaffolds are based on a relatively narrow set of ligand platforms. This work focusses on the synthesis as well as versatile oxidation, addition and coordination chemistry of geometrically distorted P(III) species featuring a synthetically modular, nonsymmetric trisamine platform.image