Syntheses of mixed-ligand tetranuclear gold(I)-nitrogen clusters by ligand exchange reactions with the dinuclear gold(I) formamidinate complex Au(2)(2,6-Me2Ph-form)2.
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.
Abdou
Hanan E
HE
Laboratory for Molecular Structure and Bonding, Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, USA.
Mohamed
Ahmed A
AA
Fackler
John P
JP