Azo-containing tertiary phosphines: synthesis, reactivity and structural characterisation

Aryldiazonium Salts as Nitrogen‐Based Lewis Acids: Facile Synthesis of Tuneable Azophosphonium Salts

“…[11] Surprisingly,t o date the corresponding azoammonium salts [RN 2 (NR 3 )][X] are unknown, [12] while the phosphine-diazonium Lewis adducts have been barely studied. [15,16] Flower and co-workers synthesized B,b ut only reported its 31 PNMR resonance (d 31 P{ 1 H} = 40 ppm;R= 6-naphthalen-2-ol), [17] and Wokaun and co-workers characterized C only spectroscopically (R = Cl, CN,S O 2 NH 2 ,C (O)OEt;F igure 2). [14] Later, Yasui and co-workers found that aryldiazonium tetrafluoroborates are readily dediazoniated by triphenylphosphine by single-electron transfer when mixed in alcoholic solvents at room temperature.…”

“…Later, Yasui and co‐workers found that aryldiazonium tetrafluoroborates are readily dediazoniated by triphenylphosphine by single‐electron transfer when mixed in alcoholic solvents at room temperature . Flower and co‐workers synthesized B , but only reported its 31 P NMR resonance ( δ 31 P{ 1 H}=40 ppm; R=6‐naphthalen‐2‐ol), and Wokaun and co‐workers characterized C only spectroscopically (R=Cl, CN, SO 2 NH 2 , C(O)OEt; Figure ) . Herein, we report on the facile synthesis of readily tuneable azophosphonium salts simply from phosphines and aryldiazonium tetrafluoroborates in acetonitrile, and provide detailed mechanistic insight by experimental and computational means.…”

Palladium complexes with bis(diphenylphosphinomethyl)amino ligands and their application as catalysts for the Heck reaction

“…Especially, chiral phosphine ligands which have nitrogen and their Pd(II) complexes have become increasingly important due to their improved catalytic activity [8][9][10]. The nature of the phosphine ligand coordinated to the metal influences the stability of the catalysts and the rate of the catalyzed reactions [11][12][13].…”

Facile Synthesis of Tuneable Azophosphonium Salts

“…Four decades later, Wokaun and co‐workers observed a red colour upon addition of tris(dimethylamino)phosphine to aromatic diazonium tetrafluoroborate salts and characterised the formed adducts ( D ) spectroscopically [R′ = N(Me) 2 , R = p ‐Cl, o ‐Cl, o ‐CH 3 + p ‐Cl, p ‐C(O)OEt, p ‐SO 2 NH 2 , p ‐CN] . Subsequently, Flower and co‐workers reported the 31 P{ 1 H} NMR chemical shift of E ( δ 31 P{ 1 H} = 40; R = 6‐naphthalen‐2‐ol) . Very recently, the investigation of azophosphonium salts has picked up interest.…”