On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates

The ambiphilic nature of geometrically constrained Group 15 complexes bearing the N , N ‐bis(3,5‐di‐ tert ‐butyl‐2‐phenolate)amide pincer ligand (ONO 3− ) is explored. Despite their differing reactivity towards nucleophilic substrates with polarised element–hydrogen bonds (e.g., NH 3 ), both the phosphorus(III), P(ONO) ( 1 a ), and arsenic(III), As(ONO) ( 1 b ), compounds exhibit similar reactivity towards charged nucleophiles and electrophiles. Reactions of 1 a and 1 b with KO t Bu or KNPh 2 afford anionic complexes in which the nucleophilic anion associates with the pnictogen centre ([( t BuO)Pn(ONO)] − (Pn=P ( 2 a ), As ( 2 b )) and [(Ph 2 N)Pn(ONO)] − (Pn=P ( 3 a ), As ( 3 b )). Compound 2 a can subsequently be reacted with a proton source or benzylbromide to afford the phosphorus(V) compounds ( t BuO)HP(ONO) ( 4 a ) and ( t BuO)BzP(ONO) ( 5 a ), respectively, whereas analogous arsenic(V) compounds are inaccessible. Electrophilic substrates, such as HOTf and MeOTf, preferentially associate with the nitrogen atom of the ligand backbone of both 1 a and 1 b , giving rise to cationic species that can be rationalised as either ammonium salts or as amine‐stabilised phosphenium or arsenium complexes ([Pn{ON(H)O}] + (Pn=P ( 6 a ), As ( 6 b )) and [Pn{ON(Me)O}] + (Pn=P ( 7 a ), As ( 7 b )). Reaction of 1 a with an acid bearing a nucleophilic counteranion (such as HCl) gives rise to a phosphorus(V) compound HPCl(ONO) ( 8 a ), whereas the analogous reaction with 1 b results in the addition of HCl across one of the As−O bonds to afford ClAs{(H)ONO} ( 8 b ). Functionalisation at both the pnictogen centre and the ligand backbone is also possible by reaction of 7 a / 7 b with KO t Bu, which affords the neutral species ( t BuO)Pn{ON(Me)O} (Pn=P ( 9 a ), As ( 9 b )). The ambiphilic reactivity of these geometrically constrained complexes allows some insight into the mechanism of reactivity of 1 a towards small molecules, such as ammonia and water.