Gold(I) Complexes with N-Donor Ligands. 2. Reactions of Ammonium Salts with [Au(acac-κ<i>C</i>²)(PR₃)] To Give [Au(NH₃)L]⁺, [(AuL)₂(μ₂-NH₂)]⁺, [(AuL)₄(μ₄-N)]⁺, or [(AuL)₃(μ₃-O)]⁺. A New and Facile Synthesis of [Au(NH₃)₂]⁺ Salts. Crystal Structure of [{AuP(C₆H₄OMe-4)₃}₃(μ₃-O)]CF₃SO₃

The complexes [Au(acac-κC2)(PR3)] (acac = acetylacetonate, R = Ph, C6H4OMe-4) react with (NH4)ClO4 to give amminegold(I), [Au(NH3)(PR3)]ClO4, amidogold(I), [(AuPR3)2(μ2-NH2)]ClO4, or nitridogold(I), [(AuPR3)4(μ4-N)]ClO4, complexes, depending on the reaction conditions. Similarly, [Au(acac-κC2)(PPh3)] reacts with (NH3R‘)OTf (OTf = CF3SO3) (1:1) or with [H3N(CH2)2NH2]OTf (1:1) to give (amine)gold(I) complexes [Au(NH2R‘)(PPh3)]OTf (R‘ = Me, C6H4NO2-4) or [(AuPPh3)2{μ2-H2N(CH2)2NH2}](OTf)2, respectively. The ammonium salts (NH2R‘2)OTf (R‘ = Et, Ph) react with [Au(acac-κC2)(PR3)] (R = Ph, C6H4OMe-4) (1:2) to give, after hydrolysis, the oxonium salts [(AuPR3)3(μ3-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(μ3-O)]OTf·Me2CO (R = C6H4OMe-4) has been determined: triclinic, space group P1̄, a = 14.884(3) Å, b = 15.828(3) Å, c = 16.061(3) Å, α = 83.39(3)°, β = 86.28(3)°, γ = 65.54(3)°, R1 (wR2) = 0.0370 (0.0788). The [(AuPR3)3(μ3-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° and Au···Au contacts in the range 2.9585(7)−3.0505(14) Å. These cations are linked into centrosymmetric dimers through two short Au···Au [2.9585(7), 3.0919(9) Å] contacts. The gold atoms of the dimer form a six-membered ring with a chair conformation.