On the redox reactivity of a geometrically constrained phosphorus(III) compound

The reactivity of a geometrically constrained phosphorus(III) complex bearing the N,N-bis(3,5-di-tert-butyl-2-phenolate)amide pincer ligand towards oxidants and reductants is explored. This compound can be readily oxidized to the phosphorus(V) dihalo-derivatives P(ONO)X2 (X = Cl (2), Br (3) and I (4)). Attempts at isolating the analogous difluoride were unsuccessful yielding only the hydrofluoride P(ONO)(H)F (5), however P(ONO)F2 (6) can be accessed via a halide exchange reaction of 2 with KF. Compound 2 can be employed as a precursor to novel cationic species through chloride ion displacement. Reaction of 2 with two or three molar equivalents of dimethylaminopyridine (DMAP) affords [P(ONO)(Cl)(DMAP)2]+ (7) and [P(ONO)(DMAP)3]2+ (8). Reaction of 2 with 2,2'-bipyridine (bipy) affords [P(ONO)(Cl)(bipy)]+ (9), although this species was only accessible upon addition of a halide abstracting agent. The dicationic tris(pyridine) adduct [P(ONO)(py)3]2+ (10) is also accessible by reaction of 4 with pyridine. Oxidation of 1 using oxygen gas proceeds slowly and allows for the observation of two compounds, a mixed valence dimeric phosphorus(III)/phosphorus(V) (11) and the fully oxidized species (12). Finally, reaction of 1 using potassium graphite results in the dimerization of the putative radical anion through formation of a P-P bond to afford [P(ONO)]22- (13). Reactions with TEMPO result in the formation of the trigonal bipyramidal species P(ONO)(TEMPO)2 (14).