Synthesis and transition metal chemistry of new bromo- and alkyl substituted phosphinite ligands

Article abstract of DOI:10.1016/j.poly.2012.02.016

Ligands Ph₂P(OAr) (Ar = 2,4,6-C₆H₂Br ₃, 1; Ar = C₆H₃(o-OMe)(p-C₃H ₅), 2) were prepared by treating PPh₂Cl with tribromo phenol and eugenol, respectively, in good yields. The reaction of Ph ₂P(OAr) with [Pd(COD)Cl₂] in 2:1 molar ratio yielded trans-[Pd{PPh₂(OAr)}Cl₂] (4) and cis-[Pd{PPh ₂(OAr)}Cl₂] (5), respectively. The chloro-bridged dipalladium complex [Pd₂{PPh₂(OAr)}₂Cl ₄] (6) was obtained in the 1:1 reaction between 2 and [Pd(COD)Cl ₂], along with 5 as a minor product. Mononuclear complexes, [Au{PPh₂(OAr)}Cl] (Ar = 2,4,6-C₆H₂Br ₃, 7; Ar = C₆H₃(o-OMe)(p-C₃H ₅), 8) and [(Ru(η⁶-p-cym){PPh₂(OAr)}Cl ₂] (9) were prepared by reacting ligands 1 and 2 with [AuCl(SMe ₂)] and [(Ru(η⁶-p-cym)Cl₂]₂, respectively. All the complexes were characterized by ³¹P, ¹H NMR and elemental analyses data.