POLYHEDRON, vol.28, no.12, pp.2313-2320, 2009 (SCI-Expanded)
Two new bis(diphenylphosphino)isopropylphenylamines, (PPh2)(2)N-C6H4-CH(CH3)(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 (Ph2P=E)(2)N-C6H4-CH(CH3)(2), where E = O, S or Se, respectively. The palladium and platinum complexes [M{(Ph2P)(2)N-C6H4-CH(CH3)(2))Cl-2] (M = Pd, Pt) and the copper complex [Cu((Ph2P)(2)N-C6H4-CH(CH3)(2))(2)]PF6 were isolated from the reaction of the bis(phosphino)anilines with MCl2(cod) or [Cu(CH3CN)(4)]PF6, 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.