New organogold chemistry. I. Synthesis and fluorine-19 nuclear magnetic resonance studies of some fluoroorganogold compounds

Abstract

no racemization occurred either during chromatography of the liquid acetate, or drying at 55°( 1 mm).Kinetic Methods. Du Pont glacial acetic acid was purified according to the procedure described by Wiberg.41 Approximately 0.5 g of ferrocenyl alkyl tosylate was dissolved in 50.00 ml of purified acetic acid. Aliquots (5.00 ml) were then added to each of nine previously prepared constricted tubes which were fitted with a 19/38 joint. The tubes were stoppered, cooled to -196°, then attached to a degassing apparatus. Three freeze-thaw degassing cycles at 1 µ were carried out, after which the tubes were sealed at the constriction. The samples were then thermostated. Ampoules were withdrawn at various intervals, quenched by shaking in an ice slush, and opened. The contents were poured into a beaker containing a small amount of purified acetic acid. The ampoule (41) K. Wiberg, "Laboratory Technique in Organic Chemistry,"McGraw-Hill Book Co., Inc., New York, N. Y" 1960, p 249. was rinsed three times with acetic acid and the washings were added to the beaker. The acetic acid solution was then titrated with 0.2 N sodium acetate in acetic acid; the end point was determined from a potentiometric plot. Rate constants were obtained from a leastsquares fit of the data to the first-order rate expression.Solvolysis Products. Acetolysis containing about 0.5 g of ferrocenylalkyl tosylate in 10 ml of purified acetic acid were degassed according to the above procedure. After ten half-lives in a sealed ampoule at the desired temperature, the reaction mixture was added to excess dry pyridine. The solvent was then evaporated at room temperature (1 mm), and the resulting oil was chromatographed on grade III, neutral alumina. Unrearranged acetates were obtained in yields of 90%, and identified by comparison of their infrared and nmr spectra with those of authentic samples.

Organogold(I) complexes: Synthesis, X-ray crystal structures and aurophilicity

“…The major improvement in the field was the preparation of mono and polyfluoro aryl gold compounds, especially neutral complexes of the ''Ar F AuL'' [9] type. Many reports in the literature concern fluorinated derivatives such as 2,4,6-tris(trifluoromethyl)phenylgold(I) complexes [8,[10][11][12][13] with various ligands like triphenylarsine or diphosphines for examples. The presence of a ''Ar F '' fluoroaryl group provides greater stability compared to aryl analogs.…”

“…We report the synthesis of gold(I) complexes with good overall yields from commercially available chloro(triphenylphosphine)gold(I). 13 C NMR spectra properties for complexes 1, 2, 4, 6, 7 and 8 had particular features, with a large coupling constant between the ipso-carbon and the phosphorous atom. However, in complexes 3 and 5 the ipso-carbon could not be identified.…”

“…13 C NMR spectrum of complex 1. To establish this coupling by 13 C NMR, the CDCl 3 solution in the NMR tube must be very concentrated (100 to 120 mg of the complex to reveal this small doublet).…”

A complex of gold(I) benzenethiolate with isocyanide: synthesis and crystal and molecular structures

“…The yield of complex 3 was 1. Gold benzenethiolate (6). A solution of benzenethiol (2.26 g, 20.5 mmol) in methanol (8 mL) was added for 5 min to a stirred solution of HAuCl 4 •3H 2 O (2.10 g, 5.33 mmol) in a mixture of water (12 mL) and methanol (61 mL).…”

“…4 At the same time, gold(I) chloride is known to form the complexes RNCAuCl with both aryl and alkyl isocyanides. [5][6][7] These data suggest that the stability of complexes of the type 1 depends, at least, on two factors: the electrone gativity of the acido ligand (X) and the π withdrawing properties of the isocyanide ligand.…”