Gold m Complexes

The cationic dinuclear oxo-gold(m) complexes of substituted bipyridyls react with olefins to give the stable coordination compounds shown in Scheme 79. The reactions are often incomplete, produce many byproducts, and give low yields of the olefin complexes/... 

Arylmercury compounds are also often used as starting materials for the synthesis of palladium(ll) complexes. These reactions, whose reagents and products are compiled in Table 3, typically involve the use of chloromercurio derivatives with palladium chloride complexes (entries a-d). 93>95>179-i8i Similar procedures have been applied to the synthesis of ruthenium(ll) and gold(m) complexes (entries e and f).181,182... 

Aza-analogues of oxygen compounds frequently show related reactivity patterns, and this is certainly seen in a comparison of the chemistry of imines and carbonyl compounds. For example, 1,3-diimines are readily deprotonated to yield the 1,3-diketonate analogues. The most frequent consequence of this is that reactions which are expected to yield 1,3-diimine complexes often lead to those of the deprotonated species. This is seen in the formation of the gold(m) complex of a deprotonated macrocycle in the reaction of 1,2-diaminoethane with 2,4-pentanedione in the presence of Na[AuCl4] (Fig. 5-4). The exact sequence of events in this reaction is not known, but note that the product is a square-planar gold(in) complex of the doubly-deprotonated macrocycle, rather than a gold(i) species ... 

Figure 5-4. The template formation of a gold(m) complex of a dianionic macrocycle...

Gold(m) complexes have been obtained by using a chelating diarsine ligand from the reaction with sodium tetrachloroaurate(m) in presence of sodium iodide. The iodide [Au(diars)2I2]I and other cations, [Au(diars)2l]2+ and [Au(diars)2]3 +, can be obtained. It is held that these are species with six, five and four coordination for Au111 with octahedral,33 trigonal bipyramidal and planar structures, respectively. Chelating phosphine complexes also exist. 

Perhalogenoaryls are more stable than the unsubstituted phenyls [176] and can be synthesized conveniently by oxidation of gold(I) complexes (demonstrating the stability of the Au-C bond). The initial product of oxidation addition seems to be the frans-isomer, which generally rearranges to the m-form ... 

Gold(I) ylides are oxidized in 0.1 M [Bu4N]BF4/THFat low potentials of +0.11 and + 0.23 V vs. Ag/AgCl (quasi-reversible). The dinuclear amidinate oxidizes under the same conditions at + 1.24 V vs. Ag/AgCl (reversible). These large differences in chemical character of the dinuclear gold(I) complexes appear to explain the widely different behavior of these compounds and especially toward the reaction with mercury cyanide. 

Laguna, A. and Laguna, M. (1999) Coordination chemistry of gold(II) complexes. Coordination Chemistry Reviews, 193-195, 837-856. 

Mohamed, A.A., Mayer, A., Abdou, H.E., Irwin, M.D., Perez, L. and Fackler, J.P. Jr (2007) Dinuclear and tetranuclear gold-nitrogen complexes. Solvent influences on oxidation and nudearity of gold... 

Abdou, H. (2006) PhD. Thesis New Chemistry with Gold-Nitrogen Complexes Synthesis and Characterization of Tetra-, Tri-, and Dinuclear Gold(I) Amidinate Complexes. Oxidative-Addition to the Dinuclear Gold (I) Amidinate, A M University, Texas. 

Rawashdeh-Omary, M.A., Omary, M.A., Fackler, J.P. Jr, Galassi, R., Pietroni, B.R. and Burini, A. (2001) Chemistry and optoelectronic properties of stacked supramolecular entities of trinuclear Gold(I) complexes sandwiching small organic acids. Journal of the American Chemical Society, 123, 9689. 

Sladek, A., Hofreiter, S., Paul, M. and Schmidbaur, H. (1995) Sodium tetraphenylborate as a phenylating agent for gold(I) complexes. Journal... 

Forward, J.M., Fackler, J.P. and Staples, R.J. (1995) Synthesis and structural characterization of the luminescent Gold(I) Complex [(MeTPAJjAulJIj. Use of NaBPha as a phenyl transfer reagent to form [(MeTPA)AuPh](BPh4) and (TPA) AuPh. Organometallics, 14, 4194—4198. 

Cinellu, M.A. and Minghetti, G. (2002) Gold(l) and gold(lll) complexes with anionic oxygen donor ligands hydroxo, 0X0 and alkoxo complexes. Gold Bulletin, 35, 11. 

Navarro, M., Vasquez, F., Sanchez-Delgado, R.A., Perez, H., Sinou, V. and Schrevel, J. (2004) Toward a Novel Metal-Based Chemotherapy against Tropical Diseases. 7. Synthesis and in Vitro Antimalarial Activity of New Gold-Chloroquine Complexes. Journal of Medicinal Chemistry, 47, 5204. 

Oyaizu, K., Ohtani, Y, Shiozawa, A., Sugawara, K, Saito, T. and Yuasa, M. (2005) Highly stable gold(III) complex with a hydantoin ligand in alkaline media. Inorganic Chemistry, 44, 6915. 

Messori, L, Abbate, F., Marcon, G., Orioli, P., Fontani, M., Mini, E., Mazzei, T., Carotti, S., O Connell, T. and Zanello, P. (2000) Gold(lll) complexes as potential antitumor agents solution chemistry and cytotoxic properties of some selected gold(III) compounds. Journal of Medicinal Chemistry, 43, 3541. 

Cao, L., Jennings, M.C. and Puddephatt, R.J. (2007) Amine-amide equilibrium in gold(III) complexes and a gold(III)-gold(I) aurophilic bond. Inorganic Chemistry,... 

Sanna, G., Pilo, M.I., Minghetti, G., Cinellu, M.A., Spano, N. and Seeber, R. (2000) Electrochemical properties of gold(III) complexes with 2,2 -bipyridine and oxygen ligands. Inorganica Chimica Acta, 310, 34. 

---