Organometallic Gold I Complexes

Only a few carbonyl complexes have been reported the long known [AuX(CO)] 

Phosphonium salts of the type Me4P+ or Ph2Me2P+, which has two carbon centers, can, after deprotonation, give the bis (ylide) species and its gold compounds 

Carbenes are speties with a divalent carbon atom with various substituents and a lone pair of electrons. Classic carbene gold complexes were synthesized in the coordination sphere of the gold atom, addition of amines or alcohols to the coordinated isocyanide ligands. N-Heterocyclic carbenes (Arduengo s carbenes) 

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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. 

Bertani, R., Michelin, R.A., Mozzon, M., Traldi, P., Seraglia, R., Busetto, L., Cassani, M.C., Tagliatesta, P. and D Arcangelo, G. (1997) Mass Spectrometric Detection of Reactive Intermediates. Reaction Mechanism of Diazoalkanes with Platinum(O) and Gold (I) Complexes. Organometallics, 16(14), 3229-3233. 

Ade, A., Cerrada, F., Contel, M., Laguna, M., Merino, P. and Tejero, T. (2004) Organometallic gold(III) and gold(I) complexes as catalysts for the 1,3-dipolar cycloaddition to nitrones synthesis of novel gold-nitrone derivatives. Journal of Organometallic Chemistry, 689(10), 1788-1795. 

Briggs, D.A., Raptis, R.G. and Fackler, J.P, Jr. (1988) The structure of benzyl (triphenyl)phosphonium chloro (pentafluorophenyl)aurate(I) an organometallic gold(I) pentafluorophenyl complex useful as anylide precursor. Acta Crystallographica, Section C Crystal Structure Communications, C44(7), 1313-1315. 

In addition, the byproduct acetylacetone is very easily separated from the other reaction product. We have shown the utility of [Au(acac)PPh3] and of PPN[Au(acac)2] [PPN = bis(triphenylphosphoranylidene)ammonium = N(PPh3)2] in the synthesis of a great variety of organometallic and coordination gold(I) complexes (see Scheme l).2 Laguna et al. have also found interesting applications for these complexes.3... 

Similar to the abovementioned silver nhc coordination compounds, carbene chemistry has also been dominant in the field of gold organometallic chemistry. Noteworthy examples include a Au(PPh3)-compound derived from tetraaminoallene, that can be rationalised in terms of a dicarbene with ylide character and which, owing to the electron-rich character of the central carbon atom, offers the potential for dimetallation products.108 Non-activated allenes and alkynes have been found by Lavallo to be readily aminated by cationic carbene gold complexes.109 For this purpose, a 2,6-diisopropylphenyl functionalized cyclic alkylaminocarbene gold(I) complex... 

Complexes of Silver(i) and Gold(i).—Only three reports have appeared on the structures of gold(i) complexes. There has been rather more interest in the stereochemistry of silver(i) two-co-ordinate linear complexes in which the metal co-ordination is sometimes augmented by weak interactions with other potential donor atoms and organometallic w-complexes have both attracted attention. 

P. Schwerdtfeger, W. Koch, H. Schwarz. Relativistic Effects in Cationic Gold(I) Complexes A Comparative Study of ab Initio Pseudopotential and Density Fimc-tional Methods. Organometallics, 14 (1995) 1284-1291. 

Gd-Rubio J, Camara V, Bautista D, Vicente J. Dinuclear alkynyl gold(I) complexes containing bridging N-heterocycHc dicarbene ligands new synthetic routes and luminescence. Organometallics. 2012 31 5414-5426. 

A Au mdssbauer study of reaction products of trimeric l-benzyl-2-gold(I)-imidazole leading to Au carbene or Au imidazoline complexes and trinuclear Au " imidazolyl derivatives. X-Ray crystal structure of [ (p-l-benzylimidazolato-N, C )Au 3l2j. Journal of Organometallic Chemistry, 470, 275-283. 

Uson, R., Royo, P. and Laguna, A. (1974) Reactions of complexes of gold(I) with bis (pentafluorophenyl)thallium(III) halides. Journal of Organometallic Chemistry, 69(3), 361-365. 

Raubenheimer, H.G., Lindeque, L. and Cronje, S. (1996) Synthesis and characterization of neutral and cationic diamino carbene complexes of gold(I). Journal of Organometallic Chemistry, 511 (1-2), 177-184. 

Desmet, M., Raubenheimer, H.G. and Kruger, G.J. (1997) Synthesis and Characterization of Thienyl Oligomeric, Carbene, and Nitrogen-Donor Complexes of Gold(I). Organometallics, 16(15), 3324-3332. 

Zhang, S.-W., Ishii, R. and Takahashi, S. (1997) Syntheses and Mesomorphic Properties of Gold(I)-Carbene Complexes. Organometallics, 16, 20-26. 

The majority of gold(I) carbene complexes are pure organometallic compounds and the are out of the scope of this work. Some halide or triphenylphosphine carbene complexes are known and they will be considered here. Nucleophilic addition of alcohols or amines to gold-coordinated isocyanides is one of the best-established methods to obtain gold carbene derivatives. The reaction of H[Au(CN)2] with propene oxide and estirene oxide yields (cyano)carbene complexes (380) avoiding the intermediate step.2257 A cyclic carbene compound is obtained by reaction of a dinuclear isocyanide with amine (Scheme 32).2258... 

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