Amine complexes of gold, part 9: gold(I) halide complexes with primary and acyclic secondary amines, and their oxidation to gold(III) derivatives

作者：Doering Cindy; Jones Peter G^*

来源：Zeitschrift Fur Naturforschung Section B-a Journal of Chemical Sciences, 2018, 73(1): 43-74.

DOI：10.1515/znb-2017-0182

• amines
• gold
• halides
• secondary interactions

The reaction of (tht)AuX (X = Cl or Br; tht = tetrahydrothiophene) with various primary amines L leads to products of the form [L2Au]X-+(-). Packing diagrams of the corresponding structures are dominated by N-H center dot center dot center dot X hydrogen bonds and (in some cases) aurophilic contacts. The cyclohexylamine derivative was already known as its dichloromethane.-solvate; we have isolated the solvent-free compound and its pentane 1/4 -solvate, which all show different packing patterns. With acyclic secondary amines, the products are more varied; LAuX and [L2Au](+)[AuX2](-) were also found. These gold(I) products were generally formed in satisfactory quantities. The attempted oxidation to Au(III) derivatives with PhICl2 or Br 2 proved impossible for the primary amine derivatives [although isopropylamine-trichloridogold(III) was obtained unexpectedly from the corresponding cyanide] and unsatisfactory for the secondary amine derivatives. Products LAuX3 and [L2AuX2](+)[AuX4](-) were identified but were formed in disappointing yields. In isolated cases protonated products (LH)(+)[AuCl4](-), (LH+)(3)[AuCl4](-)(Cl-)(2) or [(Et2N)(2)CH](+)[AuBr4](-) were formed, presumably by involvement of the dichloromethane solvent and/or adventitious water. Here also the yields were poor, and some products arose as mixtures. Direct reaction of amines with AuCl3 or (tht)AuX3 was also unsuccessful. All products were character-ized by X-ray structure analysis.

• 出版日期2018-1