Forty-Five Years of Chemical Discovery Including a Golden Quarter-Century

Abstract

Inorganic chemistry became a passion for me as a graduate student in the 1950s. It was exciting to be part of the renaissance of the discipline, and I am pleased to have contributed to its strength. Physical concepts applied to the understanding of the properties of transition metal compounds guided our work initially. In the 1970s, probably as a direct result of the world abandoning the gold standard, the chemistry of gold was awakened after a long sleep. Much of the chemistry covered in this review of our work relates to novel compounds of gold and the properties they display which have been uncovered during the last 25 years of the 20th century. Stable metal-metal bonded Au(II) and organometallic Au(III) compounds, bi- and trimetallic oxidative addition, phosphorescent species with microsecond lifetimes, gold chains resulting from aurophilic bonding stronger than H-bonding, and recently, gold binding to organic pi acids have intrigued my group and other gold chemists during this period.

Dipodal Ferrocene‐Based Adsorbate Molecules for Self‐Assembled Monolayers on Gold

“…In general, two-coordinate gold(I) compounds experience attractive aurophilic interactions if the AuÀAu separations are below 3.6 ; their strength can be up to 10 kcal mol À1 for a dimeric unit, similar to standard hydrogen bonds. [24] The energetic contribution of longer Au À Au contacts is negligible.…”

Unique distal size selectivity with a digold catalyst during alkyne homocoupling

“…The results indicate that aurophilic bonding has a positive influence on the reaction rate but none on the distal size selectivity. Since previous kinetic studies have demonstrated that the rate-determining step of the gold-catalysed homocoupling of alkynes in solution is the oxidation of gold(I) 17 , it is not surprising that aurophilic bonding improves the reaction rate by neighbouring gold atomassisted oxidation of gold(I) 26,27 . To test if aurophilic bonding has also any influence in the distal size selectivity, we prepared the digold acetylide complexes 6a [Au 2 dppe(C 10 ) 2 ] and 6b [Au 2 dppe(C 12 ) 2 ], and the results after oxidation with selectfluor were compared with those obtained before for the corresponding monogold acetylides 3a-b.…”

Gold is going forensic

“…Cocaine, heroin, morphine, and codeine are identified by microcrystal test with H [AuCl 4 ]. This test involves the addition of a 5% w/v solution of chloroauric acid in water (HAuCl 4 •3H 2 O) to a dilute aqueous acidified solution of suspected cocaine, followed by the observation of the resulting crystals microscopically of the envisaged salt (L-cocaine) [AuCl 4 ] as shown by X-ray crystallography [20,21].…”

“…The degradation product L-ecgonine has been used as a marker for recent cocaine use [27]. The structure of the hydrated gold(III) tetrachloride salt of Lecgonine, (L-ecgonine) 4 − anions. For charge balance, one of the seven water molecules has to be a hydronium ion or one of the hydroxyl groups of the cations has to be diprotonated [20,21].…”

“…As a chemical catalyst, gold plays an important role in new environmental applications, such as pollution control of mercury emissions and in fuel cells. Several interesting real-world optical applications of gold resulted in marketable optical devices [1][2][3][4][5][6][7]. Gold is emerging in a new application: gold is going forensic!…”