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

Ligands Ph2P(OAr) (Ar = 2,4,6-C6H2Br3, 1; Ar = C6H3(o-OMe)(p-C3H6), 2) were prepared by treating PPh2CI with tribromo phenol and eugenol, respectively, in good yields. The reaction of Ph2P(OAr) with Pd(COD)Cl-2] in 2:1 molar ratio yielded trans-[Pd{PPh2(OAr)}Cl-2] (4) and cis-[Pd{PPh2(OAr)}Cl-2] (5), respectively. The chloro-bridged dipalladium complex [Pd-2{PPh2(OAr)}(2)Cl-4 (6) was obtained in the 11 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-C6H2Br3, 7; Ar = C6H3(o-OMe](p-C3H5), 8) and [(Ru(eta(6)-p-cym){PPh2(OAr)Cl (2)} (9) were prepared by reacting ligands 1 and 2 with [AuCl(SMe2)] and [(Ru(eta(6)-p-cym)Cl-2](2), respectively. All the complexes were characterized by P-31. H-1 NMR and elemental analyses data. (C) 2012 Elsevier Ltd. All rights reserved