Gold complexes acetylide

Luminescent gold(l) acetylide complexes. Photophysical and photoredox properties and crystal structure of [ Au(C = CPh) 2 (p-Ph2PCH2CH2PPh2)]. Journal of the Chemical Society, Dalton Transactions, 2929-2932 (d) Che, C.-M., Wong, W.-T., Lai, T.-F. and Kwong, H.-L. (1989) Novel luminescent binuclear gold(I) isocyanide complexes. Synthesis, spectroscopy, and X-ray crystal structure of Au2(dmh)(CN)2 (dmb = 1,8-di-isocyano-p-menfhane). Journal of the Chemical Society, Chemical Communications, 243-244. 

Isonitrile)gold(I) acetylide complexes. Journal of Materials Chemistry, 5,... 

Gold(I) acetylide complexes have been prepared from alkynyllithium compounds [Eq. (22)] (63), and a dimeric complex [(PhC=C)Au(/u.-dpe)-Au(C=CPh)] [dpe = bis(diphenylphosphino)ethane] was obtained analogously. The simplest acetylide complexes are perhaps those containing only acetylide ligands. The compounds [Au(C=CPh)]x and [Au(C=C-/-Bu)]4 (1) contain cr- and 7r-bonded acetylide groups, the values of... 

CPh), the complex K[Au(C=CPh)2] was obtained, whereas the presence of excess K(C CH) yielded K2[HC CAuC=CAuC CH] and K[Au-(C CH)2], The addition of HC CCH2CR2CN (R = Me or Ph) to gold(I) iodide in liquid ammonia gave (66) the gold(I) acetylide, whose infrared spectrum indicated a d7r-p7r interaction between the gold atom and the alkynyl group. 

Figure 12.2 cis-trans conformational conversion upon formation the Au-Ln arrays by incorporating gold(I) acetylide diphosphine complexes with Ln(hfac)3 units [122], (Redrawn from H.B. Xu et al, Conformation changes and luminescent properties of Au-Ln (Ln = Nd, Eu, Er, Yb) arrays with 5-ethynyl-2,2 -bipyridine, Inorganic Chemistry, 47, 10744, 2008.)... 

Packheiser, R., Jakob, A., Ecorchard, P, Walfort, B., and Lang, H. 2008. Diphenylphosphinoferrocene gold(l) acetylides Synthesis of heterotri- and heterote-Iramelallic transition metal complexes. Organometallics 27, 1214—1226. 

The reaction of polymeric long-chain gold(I) acetylides with isocyanides results in the formation of alkynylgold(I) isocyanide complexes, as represented in equation 44, some of them displaying liquid-crystalline properties (m = 6, 8, 10, 12 X = H, OC H >h+i n = 4, 6, 8, 10). 

Takahashi and co-workers " " carried out an interesting systematic study of related liquid-crystalline isonitrile gold(i) acetylide complexes in order to lower transition temperatures and avoid the decomposition processes usually... 

Scheme 11 (a) A )i -Ti Ti -acetylide bimetallic Au catalyst (24) used in the azide-alkyne cycloaddition, (b) a gem-diaurated catalyst (25) used for the cycloaddition of dialkynes, and (c) a trimetallic gold complex (26) used in the cycloisomerisation of allenynes... 

The solid-state emission of the acetylide complexes 92a, 92b, 93a, and 93b occurs at 490, 521, 538, and 539 nm, respectively. The emission energy shows a red shift from the dimer to the trimer but is not sensitive to the methoxy substituent on the phenylacetylide ligand. In view of this, together with the large Stokes shifts observed, the excited state has been assigned to be [(d6t) (po) ] in origin. The photochemical properties of these gold(I) acetylides have also been studied. For example, the phosphorescent state of 93a has been found to be quenched by the electron acceptor 4-methoxycarbonyl-A -methylpyridinium ion. 

Gold acetylide polymers have been synthesized by two dilFerent methods. The first method was a reaction of diacetylide gold complexes with diphosphines. The second was a reaction of diethynylarenes with a diphosphine gold complex. Scheme 34 shows the reaction of the gold-containing monomer 115 with the dialkyne monomers 116 to produce polymers 117. These polymers displayed molecular weights of approximately 18,000. 

Another heterotrimetallic complex with a gold(I) acetylide imit is Ph3PAu-C=C-NCN-Pt-C=C-Fc (91), which can be obtained by combining PhsPAu-C C-NCN-PtCl (90) with FcC CSnMcs [74k]. Complex 91 represents a rigid-rod shaped molecular wire molecule in which the transition metals Au, Pt, and Fe are spanned by acetylide, cyclopentadienyl and phenylene imits. 

Qrganometallic complexes for nonlinear optics. 14. Syntheses and second-order nonlinear optical properties of ruthenium, nickel and gold o-acetylides of 1,3,5-triethynylbenzene X-ray crystal structures of 1-(HC=C)-3,5-C5H3(rrani-C=CRuCl(dppm)2)2 and l,3,5-C6H3(C=CAu(PPh3))3, I. R. Whittall, M. G. Humphrey, S. Houbrechts, J. Maes, A. Persoons, S. Schmid, D. C. R. Hockless, J. Organomet. Chem. 1997, 544, 277. 

Many complex acetylides are explosive and, as would be expected, the more labile ones are readily hydrolysed. The complexes with silver and gold in particular are sensitive to li t. Some other reactions of the complexes are reduction,... 

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