Thallium-gold interactions

The use of asymmetric bridging ligands, which permits a selective coordination of the different donor atoms to the metal centers and leads to supported gold-thallium interactions forced by the ligand. 

Reactions between basic gold(I) complexes and acid thalliumff) salts, which give rise to supramolecular networks formed via acid-base stacking containing unsupported gold-thallium interactions. 

C6C15) with dimethylsulfoxide (DMSO), which leads to the synthesis of [Tl2 Au(C6F5)2 2 p-DMSO 3] or [Tl2 Au(C6Cl5)2 2 h-DMSO 2]ra, respectively.62 The crystal structure of the complex with fluorine shows a monodimensional polymer formed by repetition of [Au--Tl(p-0 = SMe2)3Tl] units, with gold-thallium interactions of 3.2225(6)-3.5182(8), while the pentachlorophenyl derivative contains two bridging DMSO molecules and an additional [Au(C6Cl5)2] anion. In addition, a thallium-thallium interaction of 3.7562(6) A appears in the latter (Fig. 21). 

The gold-thallium interactions in these complexes are of approximately the same strength, because that they show no dependence on the behavior of the [AuR2] fragments as angular or linear bridges in the former or as linear... 

The first descriptions of heteronuclear luminescent supramolecular complexes were given by Fackler et al. in 1988 and 1989. In these studies, one gold-thallium and one gold-lead complex were reported. As in the case of the gold-silver dinuclear systems, the extended systems appeared as a result of the unidirectional polymerization of dinuclear or trinuclear units through metal-metal interactions. These were prepared by reaction of the gold precursor [PPN][Au(MTP)2] (PPN = N(PPh3)2 ... 

An example of this is the gold-thallium complex n[Au(CN)2] [69], prepared by reaction of T1N03 and K[Au(CN)2]-2H20 in the 90s by Patterson et al. This group carried out a pioneering study of the luminescence properties of this complex and their theoretical interpretation. The structure showed a complexity that made the analyses difficult. Thus, neutron diffraction studies showed thallium-gold interactions of 3.446 and 3.463 A, shorter than the sum of their van der Waals radii (3.62 A) in one of the three crystallographically-distinct Au sites in the crystal. 

Some elements found in hody tissues have no apparent physiological role, hut have not been shown in he toxic. Examples arc rubidium, strontium, titanium, niobium, germanium, and lanthanum. Other elements are toxic when found in greater than trace amounts, and sometimes in trace amounts. These taller elements include arsenic, mercury, lead, cadmium, silver, zirconium, beryllium, and thallium. Numerous irlhcr elements are used in medicine in non-nulrieni roles. These include lithium, bismuth, antimony, bromine, platinum, and gold. The interactions of mineral nutrients with carbohydrates, fats, and proteins, minerals with vitamins (qv). and mineral nutrients with toxic elements are areas of active investigation. 

As described above, among the several closed-shell metal ions that form luminescent supramolecular entities with gold, thallium(I) forms the most numerous examples. While aurophilic attractions can be considered the upper extreme of the metallophilic interactions (with values up to 46 kJ mol-1), intermetallic contacts involving T1(I) centers appear as the weakest ones (even <20 kJ mol-1),46 which is explained by the enhancement of the Au---Au interactions and the weakening of the Van der Waals attractions between the s2 metal atoms produced by the relativistic effects.47 Nevertheless, the complexes in which this interaction appears are surprisingly stable, with additional electrostatic, packing forces, or the ligand architecture, responsible for this fact. 

AuCN has a similar structure to AgCN and likewise dissolves in excess cyanide to form Au(CN)J this is important in the extraction of gold. It has been characterized as various salts (Tl, K, Bu4N, Cs) with Au-C 1.964A (Bu4N salt [91]). The thallium salt has short Au-Au (3.10A) and Au-Tl (3.50 A) interactions extended-Huckel calculations indicate the importance of relativistic effects in these covalent interactions. Isocyanides form stable complexes ... 

Our first study of these systems was the synthesis in 1998 of the polymeric complex [ 1( 6 5)2( )2] through the reaction between triphenylphosphine oxide, thallium nitrate and lithium bis(pentafluorophenyl)aurate(I) [71]. This complex consisted of an extended unsupported linear chain of alternate gold and thallium centers. These atoms displayed Au-Tl interactions of 3.0358(8) and 3.0862(8) A, and the thallium atoms showed a distorted pseudo-trigonal-bipyramidal environment, taking into account the stereochemically active inert pair of this atom. As described below, the environment around thallium is one of the main factors that affects the optical properties of these mixed systems. 

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