Theoretical Chemistry of Gold

Abstract

Gold is an element whose unique properties are strongly influenced by relativistic effects. A large body of appropriate calculations now exist and their main conclusions are summarized. The theoretical interpretation of the aurophilic attraction is discussed in detail.

The effects of Group 11 transition metals, including gold, on ethylene binding to the ETR1 receptor and growth of Arabidopsis thaliana

“…While a simplistic prediction based upon atomic mass is that Au(I) has a larger ionic radius than Ag(I), this ap- pears to be incorrect. Both theoretical calculations [27,28] and experimental data [29] show that Au(I) is actually smaller than Ag(I) because of unusually large relativistic effects in the outer electron orbitals of the gold ions [27,28,[30][31][32][33][34]. Also, unlike copper and silver ions where only the Cu(I) and Ag(I) valence states can complex with olefins, two valence states of gold form complexes with olefins so that Au(III) also binds to ethylene [30,35].…”

Fluxionality of gold nanoparticles investigated by Born-Oppenheimer molecular dynamics

“…In particular the chemistry of small gold particles has attracted much attention and its theoretical properties have been extensively reviewed [4][5][6][7]. Such interest originates from several reasons: the special catalytic activity of small clusters as compared to larger ones [8][9][10], possible application in the building of nanoscale devices [11][12][13], the special properties as semiconductors [14,15], biosensors [16], electrodes [17] and their optical properties [16,18,19].…”

Structural and Photophysical Properties of (Phosphane)gold(I)‐Decorated 4,4′‐Diethynyl‐2,2′‐bipyridine Ligands

“…[3,[9][10][11] By combining phosphine and alkyne metal-binding domains at a gold(I) centre, one gains significant scope for the design of macromolecules: [12] rigid-rod P-Au-C≡C-domains and a wide range of readily accessible mono-, bi-and polydentate phosphine ligands containing sp 3 hybridized P atoms combine with a tendency for gold atoms to aggregate (so-called 'aurophilicity'). [13][14][15]16] Of the 215 compounds in the CSD (CSD v 5.3 with May 2009 updates, Conquest v. 1.11) [17] possessing R 3 PAuC≡C units, only 19 [9,[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] exhibit intermolecular aurophilic interactions resulting in onedimensional Au...Au bonded polymers. Of particular relevance to our work is the trigold derivative ( n Bu 3 PAuC≡CCH 2 OCH 2 ) 3 CCH 2 Otpy (tpy = 2,2';6',2"-terpyridine) which forms one-dimensional chains with an oriented assembly in the solid state in which all the tpy units point in the same direction.…”

“…[15] We report here a series of 2,2'-bipyridine ligands (Chart 1), decorated in the 4 and 4'-positions with phosphine gold(I) alkynyl units, and discuss the relationship between their solid state structures and their solid state and solution emissive properties.…”