LATE TRANSITION-METAL OXO AND IMIDO COMPLEXES .11. GOLD(I) OXO COMPLEXES

The gold(I) oxo complexes [(LAu)3(mu3-O)]BF4 (1) have been prepared for L = PMePh2, PMe2Ph, PEtPh2, PPriPh2, P(p-ClPh)3, P(o-tol)3, P(OEt)Ph2, and P(OMe)3. Two of these new oxo complexes, as well as a new crystal form of [(PPh3Au)3(mu3-O)]BF4, were structurally characterized. Crystals of [(PMePh2Au)3(mu3-O)]BF4.CH2Cl2 from CH2Cl2/ether are monoclinic (P2(1)/c) with a = 11.395(2) angstrom, b = 25.901(2) angstrom, c = 16.024(3) angstrom, beta = 110.615(8)-degrees, and Z = 4. Crystals of [(PPh3Au)3(mu3-O)]BF4.1.5CH2Cl2 from CH2Cl2/ether are monoclinic (P2(1)/c) with a -14.723(3) angstrom, b = 14.808(3) angstrom, c = 25.999(3) angstrom, beta = 104.06(3)-degrees, and Z = 4. Crystals Of [(P(o-tol)3Au)3(mu3-O)]BF4.xC6H14.0.5H2O from CH2Cl2/hexane are monoclinic (P2(1)/a) with a = 14.2611(45) A, b - 27.4668(71) angstrom, c = 23.0907(81) angstrom, beta = 91.37(2)-degrees, and Z=4. The PPh3 and the PMePh2 structures consist of inversion-related edge-bridged [(LAu)3O]+ dimers held together by Au-Au interactions. The P(o-tol)3 Structure consists of isolated [(LAu)30]+ units. New oxo complexes are also formed in equilibrium mixtures of [((PPh3)Au)3(mu3-0)]BF4 and LAuCl. Oxygen-17 NMR data for 1 show chemical shifts of +19.7 to -36.0 ppm (H2O reference) with upfield shifts corresponding to increasing basicity of the phosphine, L.