Abdou Hanan E, Mohamed Ahmed A, Fackler John P
Laboratory for Molecular Structure and Bonding, Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, USA.
Inorg Chem. 2007 Jan 8;46(1):141-6. doi: 10.1021/ic0612449.
The reaction of the sterically crowded dinuclear gold(I) amidinate complex Au2(2,6-Me2Ph-form)2, 1, with the less bulky bidentate nitrogen ligands results in the formation of tetranuclear gold(I) complexes. When the less bulky amidinate, K(4-MePh-form), A, was reacted with 1 in a 1:1 stoichiometric ratio, crystals containing equal amounts of the tetranuclear and dinuclear gold(I) aryl formamidinates, Au4(4-MePh-form)4 and Au2(2,6-Me2Ph-form)2, where 2,6-Me2Ph-form = B, were found in the same unit cell, 2 x 2THF: space group P, a = 10.794(11) A, b = 14.392(15) A, c = 25.75(3) A, alpha = 82.564(17) degrees, beta = 85.443(18) degrees, gamma = 82.614(19) degrees. The reaction of K(4-MePh-form), A, and 1 in a 1:2 ratio (excess) produced the tetranuclear complex only, 3. The potassium salt of the exchanged bulky ligand, K(2,6-Me2Ph-form), formed as a byproduct. The reaction of the dinuclear gold(I) complex Au2(2,6-Me2Ph-form)2 with the 3,5-diphenylpyrazolate salt, K(3,5-Ph2pz), resulted in the formation of two tetranuclear mixed-ligand complexes, Au4(3,5-Ph2pz)2(2,6-Me2Ph-form)2 x 2THF, 4 x 2THF (space group P21/c, a = 11.5747(19) A, b = 25.497(4) A, c = 21.221(3) A, beta = 96.979(3) degrees) and Au4(3,5-Ph2pz)3(2,6-Me2Ph-form) x THF, 5 x THF (space group P21/c, a = 23.058(5) A, b = 14.314(3) A, c = 18.528(4) A, beta = 90.94(3) degrees. The block crystals from the tetranuclear complex, 4 x 2THF, contain mixed ligands with each pyrazolate ring facing an amidinate ring. The tetranuclear mixed ligand complex, 5 x THF, was isolated as needles with ligands alternating above and below the Au4 plane. The two tetranuclear mixed-ligand complexes emit at 490 and 530 nm, respectively, under UV excitation.
空间位阻较大的双核金（I）脒基配合物Au₂(2,6-Me₂Ph-form)₂（1）与位阻较小的双齿氮配体反应生成四核金（I）配合物。当位阻较小的脒基钾盐K(4-MePh-form)（A）与1以1:1化学计量比反应时，在同一晶胞（2×2THF，空间群P，a = 10.794(11) Å，b = 14.392(15) Å，c = 25.75(3) Å，α = 82.564(17)°，β = 85.443(18)°，γ = 82.614(19)°）中发现含有等量四核和双核金（I）芳基甲脒盐Au₄(4-MePh-form)₄和Au₂(2,6-Me₂Ph-form)₂（其中2,6-Me₂Ph-form = B）的晶体。K(4-MePh-form)（A）与1以1:2的比例（过量）反应仅生成四核配合物3。交换后的位阻较大配体的钾盐K(2,6-Me₂Ph-form)作为副产物生成。双核金（I）配合物Au₂(2,6-Me₂Ph-form)₂与3,5-二苯基吡唑盐K(3,5-Ph₂pz)反应生成两种四核混合配体配合物，Au₄(3,5-Ph₂pz)₂(2,6-Me₂Ph-form)₂·2THF（4·2THF，空间群P2₁/c，a = 11.5747(19) Å，b = 25.497(4) Å，c = 21.221(3) Å，β = 96.979(3)°）和Au₄(3,5-Ph₂pz)₃(2,6-Me₂Ph-form)·THF（5·THF，空间群P2₁/c，a = 23.058(5) Å，b = 14.314(3) Å，c = 18.528(4) Å，β = 90.94(3)°）。四核配合物4·2THF的块状晶体包含混合配体，每个吡唑环与一个脒基环相对。四核混合配体配合物5·THF以针状形式分离，配体在Au₄平面上方和下方交替排列。在紫外激发下，这两种四核混合配体配合物分别在490和530 nm处发光。
