Synthesis and characterization of new bis(diphenylphosphino)aniline ligands and their complexes: X-ray crystal structure of palladium(II) and platinum(II) complexes, and application of palladium(II) complexes as pre-catalysts in Heck and Suzuki cross-coupling reactions

AYDEMİR M., DURAP F., BAYSAL A., AKBA O., Gumgum B., ÖZKAR S., ...More

POLYHEDRON, vol.28, no.12, pp.2313-2320, 2009 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 28 Issue: 12
  • Publication Date: 2009
  • Doi Number: 10.1016/j.poly.2009.04.033
  • Title of Journal : POLYHEDRON
  • Page Numbers: pp.2313-2320


Two new bis(diphenylphosphino)isopropylphenylamines, (PPh(2))(2)N-C(6)H(4)-CH(CH(3))(2), having the isopropyl substituent at the carbon atom 2 (1) or 4 (2), were prepared by the aminolysis of chlorodiphenylphosphine with isopropyl substituted aniline at the ortho- or para-position, respectively, under anaerobic conditions. Oxidation of 1 and 2 with either aqueous hydrogen peroxide, elemental sulfur or grey selenium in thf gave the corresponding oxides, sulfides and selenides (Ph(2)P=E)(2)N-C(6)H(4)-CH(CH(3))(2), where E = O, S or Se, respectively. The palladium and platinum complexes [M{(Ph(2)P)(2)N-C(6)H(4)-CH(CH(3))(2))Cl(2)] (M = Pd, Pt) and the copper complex [Cu((Ph(2)P)(2)N-C(6)H(4)-CH(CH(3))(2))(2)]PF(6) were isolated from the reaction of the bis(phosphino)anilines with MCl(2)(cod) or [Cu(CH(3)CN)(4)]PF(6), respectively. The new compounds were characterized by NMR, IR spectroscopy and elemental analysis. Furthermore, the solid-state structures of two representative complexes were determined using single crystal X-ray diffraction analysis. The compounds of palladium (1d) and platinum (1e), both mononuclear complexes, crystallize in the monoclinic P2(1)/c space group. In both compounds the metal ion has a distorted square-planar coordination geometry. The structural properties of complexes Id and le in the solid state are very similar. The palladium complexes were also tested for their catalytic activities in C-C coupling reactions. (C) 2009 Elsevier Ltd. All rights reserved.