Gold(I) complexes with N-donor ligands .2. Reactions of ammonium salts with [Au(acac-kappa C-2)(PR3)] to give [Au(NH3)L](+), [(AuL)(2)(mu(2)-NH2)](+), [(AuL)(4)(mu(4)-N)](+), or [(AuL)(3)(mu(3)-O)](+). A new and facile synthesis of [Au(NH3)(2)](+) salts. Crystal structure of [{AuP(C6H4OMe-4)(3)}(3)(mu(3)-O)]CF3SO3

The complexes [Au(acac-kappa C-2)(PR3)] (acac = acetylacetonate, R = Ph, C6H4OMe-4) react with (NH4)ClO4 to give amminegold(I), [AuO(NH3)(PR3)]ClO4, amidogold(I), [(AuPR3)(2)(mu(2)-NH2)]ClO4, or nitridagold(I), [(AuPR3)(4)-(mu(4)-N)]ClO4, complexes, depending an the reaction conditions. Similarly, [Au(acac-kappa C-2)(PPh3)] reacts with (NH3R')OTf (OTf = CF3SO3) (1:1) or with [H3N(CH2)(2)NH2]OTf (1:1) to give (amine)gold(I) complexes [Au-(NH2R')(PPh3)]OTf (R' = Me, C6H4NO2-4) or [(AuPPh3)(2){mu(2)-H2N(CH2)(2)NH2)](OTf)(2), respectively. The ammonium salts (NH2R'(2))OTf (R' = Et, Ph) react with [Au(acac-kappa C-2)(PR3)] (R Ph, C6H4OMe-4) (1:2)to give, after hydrolysis, the oxonium salts [(AuPR3)(3)(mu(3)-O)]OTf (R = Ph, C6H4OMe-4). When NH3 is bubbled through a solution of [AuCl(tht)] (tht = tetrahydrothiophene), the complex [Au(NH3)(2)]Cl precipitates. Addition of [Au-(NH3)(2)]Cl to a solution of AgClO4 or TlOTf leads to the isolation of [Au(NH3)(2)]ClO4 or [Au(NH3)(2)]OTf, respectively. The crystal structure of [(AuPR3)(3)(mu(3)-O)]OTf.Me2CO (R = C6H4OMe-4) has been determined: triclinic, space group P (1) over bar, a = 14.884(3) Angstrom, b = 15.828(3) Angstrom, c = 16.061(3) Angstrom,alpha = 83.39(3)degrees, beta = 86.28(3)degrees, gamma = 65.54(3)degrees, R1 (wR2) = 0.0370(0.0788). The [(AuPR3)(3)(mu(3)-O)](+) cation shows an essentially trigonal pyramidal array of three gold atoms and one oxygen atom with O-Au-P bond angles of ca. 175 degrees and Au ... Au contacts in the range 2.9585(7)-3.0505(14) Angstrom, These cations are linked into centrosymmetric dimers through two short Au ... Au [2.9585(7), 3.0914(9) Angstrom] contacts. The gold atoms of the dimer form a six-membered ring with a chair conformation.