title: Pd(II) coordinated deprotonated diphenyl phosphino amino pyridine: reactivity towards solvent, base, and acid.
abstract: The reactivity and stability of P(III)-N and P(III)≈N bonds will be different towards various solvents, bases, and acids because of their difference in bond strength due to different N-pπ-P-dπ donor bonding. For this, a P≈N containing Pd(II) complex, [Pd(DPAP)2] (C1), was synthesized from the reaction between PdCl2(COD) (COD = 1,4-cyclooctadiene) and 2 equiv. DPAP (diphenyl phosphino amino pyridine) ligand, followed by deprotonation of the N-H proton of the coordinated DPAP. The reactivity and stability of coordinated P≈N in complex C1 were determined in various protic and aprotic solvents, bases, and acids. The inertness of coordinated P=N towards various solvents and bases was observed, whereas protonation occurs at the nitrogen of P=N in the presence of an acid to form P-NH, with the generation of dicationic palladium complexes (C2). The dicationic complex C2 is found to be stable in the presence of bulky monoanionic Sn(IV) reagents, whereas, in the presence of more nucleophilic anions like Br(-) or I(-), dissociation of one DPAP ligand from dicationic Pd(II) complexes C2 leads to the generation of Pd(DPAP)X2 (X = Br(-), I(-)). Finally, the utility of the complexes towards Suzuki coupling of various aryl bromides and aryl or heteraryl boronic acids has been checked.
authors.affiliation: Department of Chemical Sciences, Tezpur University, Napaam, 784028, Assam, India. spratihar@tezu.ernet.in spratihar29@gmail.com.
authors.forename: Sanjay
authors.initials: S
authors.lastname: Pratihar
authors.forename: Rupa
authors.initials: R
authors.lastname: Pegu
authors.forename: Ankur Kanti
authors.initials: AK
authors.lastname: Guha
authors.forename: Bipul
authors.initials: B
authors.lastname: Sarma