Calculated structures of SAu₃⁺and S(AuPH₃)₃₊

Abstract

Pseudopotential ab initio calculations on SAu3+ and S(AuPH&+ closely reproduce the experimental Au-S-Au angles of monomeric S(AuPR3)3+ (PR3 = PPh3, PPri3) if both correlation and relativistic effects are included.

Perfluoroarylgold complexes

“…Two of these pairs of parameters are in the normal range observed for related sulfur-centered derivatives [27][28][29][30] (Au· · ·Au 2.990(1)-3.420(1)Å; Au-S-Au 79.5(1)-95.0(3) • ). All these Au· · ·Au and Au-S-Au values are similar to those calculated for S(AuPH 3 ) 3 + using relativistic potentials (Au· · ·Au 3.05, 3.52Å; Au-S-Au 82.3, 98.5 • ) [31].…”

“…31 P{ 1 H} NMR data seem to indicate that the dinuclear product is a mixture of three isomers. In the crystal structure of the trinuclear product, the structure of the ligand allows the three bulky Au(C 6 F 5 ) 3 units to be coordinated at the same time, and shows very long Au-Au distances (the shortest one 7.095Å), which precludes any form of metal-metal bonding.…”

“…31 P{ 1 H} NMR data in CDCl 3 even at −60 • C show that the dpmp derivative is a mixture of two isomers because of Scheme 21. the coordination of gold to the central or the lateral phosphorus, although it would appear that only the first isomer crystallizes at −18 • C. The addition of a second equivalent of [Au(C 6 F 5 ) 3 (tht)] to [Au(C 6 F 5 ) 3 (dpmp)] or the same reaction in 2:1 ratio evolves cleanly to the formation of a unique derivative, [{Au(C 6 F 5 ) 3 } 2 (-dpmp)], which presumably displays the Au(C 6 F 5 ) 3 fragments coordinated to the most external phosphorus [119] (see Scheme 21). This complex reacts with [AuX(tht)] (X = Cl, C 6 F 5 ) to give the mixed-valence Au I -Au III -Au I complexes [{Au(C 6 F 5 ) 3 } 2 ( 3 -dpmp)AuX] [119].…”

Trans-Pacific Air Pollution

“…Unfortunately, there are insuffi-nent reaches North America episodically. At Cheeka Peak Observatory on the coast of Washington State, Jaffe and co-workers (7) have observed five springtime Asian pollution events since 1997. At Tagish in the Canadian Rocky Mountains, Bailey et al (8) detected elevated levels of pesticides (lindane, chlordane, and DDT) during winter and spring and attributed them to pollution transported from continental Asia.…”

The aurophilicity phenomenon: A decade of experimental findings, theoretical concepts and emerging applications

“…The introduction of relativistic effects in more advanced calculations in the 1970s has shown that bonding between closed-shell metal atoms or ions may be strongly enhanced by these effects (56)(57)(58)(59)(60)(61)(62). Since relativistic effects have been known to be particularly strong for the heavy elements in the Periodic Table in general, and to reach a local maximum for gold in particular (6, 7), aurophilicity was accepted as a logical consequence of these contributions (5).…”