Gold complexes of 3,4-bis(diphenylphosphinoamino)toluene and 1,2-bis(diphenylphosphinoamino)benzene.: A comparative study

The reaction of the diphosphines 3,4-(NHPPh(2))(2)MeC(6)H(3) and 1,2-(NHPPh(2))(2)C(6)H(4) with gold(I) and gold(III) substrates such as [Au(C(6)F(5))(n)(tht)] or [Au(tht)(2)]X in various molar ratios led to the dinuclear [RC(6)H(3){NHPPh(2)Au(C(6)F(5))(n)}(2)] (R=Me, n =1 1 or 3 6; R=H, n=1 2 or 3 7) and [{RC(6)H(3)(NHPPh(2))(2)Au}(2)][O(3)SCF(3)](2) (R=Me 3 or H 5) or the mononuclear [MeC(6)H(3)(NHPPh(2))(2)Au(C(6)F(5))(3)] 8 and [{MeC(6)H(3)(NHPPh(2))(2)}(2)Au] X (X=O(3)SCF(3) 4a or ClO(4) 4b) complexes, showing different selectivity depending on the phosphine. Reaction of 8 with gold(1) compounds gave the mixed neutral gold(I)-gold(III) [MeC(6)H(3)(NHPPh(2))(2)Au(C(6)F(5))(3)AuX] (X=Cl 9 or C(6)F(5) 10) derivatives. When the pentafluorophenyl gold precursors are treated with the disulfides 3,4-(NHPPh(2)S)(2)MeC(6)H(3) and 1,2-(NHPPh(2)S)(2)C(6)H(4) only the dinuclear complexes [RC(6)H(3)(NHPPh(2)SAu(C(6)F(5))(n))(2)] (R=Me, n =1 11 or 3 12; R=H, n =1 13 or 3 14) are obtained. Mononuclear cationic complexes [RC(6)H(3)(NHPPh(2)S)(2)Au(C(6)F(5))(2)]ClO(4) (R=Me 15 or H 16) have also been obtained by reaction of the phosphinosulfides with the gold(III) precursor [Au(C(6)F(5))(2)(OEt(2))(2)]ClO(4). The addition of the deprotonating agent NBu(4)(acac) to 1, 2 and 7 removes one aminic proton, yielding the dinuclear anionic complexes [NBu(4)][RC(6)H(3){NHPPh(2)Au(C(6)F(5))(n) }{NPPh(2)Au(C(6)F(5))(n)}] (R=Me, n =1 17; R=H, n=1 18 or 3 19). Addition of the aurating agent [Au(OClO(3))(PPh(3))] to complex 19 led to the neutral trinuclear complex [C(6)H(4){NHPPh(2)Au(C(6)F(5))(3)}{N(AuPPh(3))PPh(2)Au(C(6)F(5))(3)}] 20, containing a P,P,N-tridentate ligand. The crystal structures of complexes 1, 3, 4b, 6, 12 and 20 have been established by X-ray diffraction studies.