AuCl(SMe 2 )] reacts with HCtCR (R ) bpyl ) 2,2′-bipyridine-5-yl (1), phtpyl ) phenyl-4-(2,2′: 6′,2′′-terpyridine-4-yl) (2)) and NEt 3 (1:1:3) to afford the polymers [Au(CtCR)] n (R ) bpyl (3), phtpyl (4)). The new alkyne HCtCphccbpyl (5, phccbpyl ) 4-C 6 H 4 CtCbpyl) has been prepared by Sonogashira coupling of 4-Me 3 SiCtCC 6 H 4 I and 1 followed by desilylation of the resulting alkyne 4-Me 3 SiCtCphccbpyl. The alkynyl Au(I) complexes [Au(CtCR)L] (R ) bpyl, L ) PPh 3 (6), PTol 3 (7, Tol ) 4-MeC 6 H 4 ), PEt 3 (8); R ) phtpyl, L ) XyNC ( 9), PPh 3 (10); R ) phccbpyl, L ) PPh 3 ( 11)) have been prepared by reacting: (1) 3 or 4 with L or (2) the corresponding alkyne 1, 2, or 5 with [Au(acac)(PPh 3 )] (acac ) acetylacetonato). The reaction of 3 or 4 with diphosphines gives [{Au(CtCR)} 2 (µ-Ph 2 P(CH 2 ) x PPh 2 )] (R ) bpyl, x ) 1 (12), 2 (13), 4 (14), 10 (15); R ) phtpyl, x ) 10 ( 16)). ESI mass spectrometric studies show that complexes 12-14 are in equilibrium with the salts [Au 3 (CtCbpyl) 2 (µ-Ph 2 P(CH 2 ) x PPh 2 ) 2 ][Au(CtCbpyl) 2 ], although only when x ) 1 ( 17) was a significant concentration of the salt detected by NMR spectroscopy and isolated. The anionic complexes PPN[Au(CtCR) 2 ] (R ) bpyl ( 18), phtpyl ( 19), or phccbpyl ( 20)) have been prepared by reaction of the corresponding alkynes with PPN[Au(acac) 2 ]. Complexes 6, 10, 13, 14, 17, and 18 have been characterized by single-crystal X-ray diffraction studies. The alkynyl complexes are luminescent at room temperature, displaying dual emissions.

The reaction of (PhCH2PPh3)2[Pd(R1)Cl(μ-Cl)]2 (1; R1 = 6-formyl-2,3,4-trimethoxyphenyl) with PhC⋮CPh gives a 6.5:1 mixture of 4,5,6-trimethoxy-2,3-diphenylindenone (2)and 4,5,6-trimethoxy-2,3-diphenyl-1H-indenol (3). When the same reaction is carried out with MeO2CC⋮CCO2Me or with Me3SiC⋮CSiMe3, the compounds 4,5,6-trimethoxy-2,3-bis(methoxycarbonyl)indenone (4) and R1C⋮CSiMe3 (5) are obtained, respectively. The reactions of PhC⋮CPh with [Pd(R1)Cl(bpy)] (6; bpy = 2,2‘-bipyridine), in the presence of AgClO4, or with [Pd(R1)(MeCN)(bpy)]ClO4 (7) yield 3 and [Pd(μ-OH)(bpy)]2(ClO4)2 (8a). If 7 reacts with PhC⋮CPh under anhydrous conditions, the indenone 2 is obtained. The complex [Pd(R2)(MeCN)(bpy)]ClO4 (9; R2 = 2-formyl-3,4,5-trimethoxyphenyl) reacts with PhC⋮CPh, giving 5,6,7-trimethoxy-2,3-diphenyl-1H-indenol (10) or, under anhydrous conditions, 5,6,7-trimethoxy-2,3-diphenylindenone (11). A 1:1 mixture of both compounds is obtained by reacting [Pd(η2-R2)(μ-Cl)]2 (12) with PhC⋮CPh. [Pd(η2-R3)(bpy)](CF3SO3) (13; R3 = 6-acetyl-2,3,4-trimethoxyphenyl) reacts with the alkynes RC⋮CR‘ (R = R‘ = Ph, 4-tolyl, CO2Me, Me, Et; R = Ph, R‘ = CO2Et, 4-nitrophenyl, 4-methoxyphenyl, Me; R = tBu, R‘ = H, Me), yielding [Pd(μ-OH)(bpy)]2(CF3SO3)2 (8b) and 1-methylindenols 14−24. The catalytic reaction of [Hg(R1)2] with PhC⋮CPh and CuCl2 in the presence of Q2[Pd2Cl6] (1:6:2:0.05; Q = Me4N, PhCH2PPh3) gives the indenol 3 in 62% yield with respect to the group R present in the mercurial compound. When a similar reaction (Q = PhCH2PPh3) is carried out under nitrogen, the spirocyclic compound 10-formyl-6,7-dimethoxy-1,2,3,4-tetraphenylspiro[4.5]1,3,6,9-decatetraen-8-one (26) is obtained.

The mercuriation of 3,4,5-trimethoxy(N-tert-butylcarbamoyl)benzene with mercury(II) acetate and subsequent reaction with KCl leads to the formation of [Hg{C 6 The reaction of 2 with [PdCl 2 (MeCN) 2 ] and 2,2′-bipyridine (bpy) affords [Pd(C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4)Cl(bpy)] (3), which reacts with Tl(CF 3 SO 3 ) giving [Pd-{C 6 H{C(O)NHBu t }}(bpy)](CF 3 SO 3 ) (4). Complex 2 reacts with [PdCl 2 (MeCN) 2 ] and acetylenes RCtCR to give metallic palladium and the spirocyclic compound 10-(N-tert-butylcarbamoyl)-6,7-dimethoxy-1,2,3,4-tetraphenylspiro[4.5]-1,3,6,9-decatetraen-8-one (5) when R ) Ph or the monoinserted palladium complex [Pd{C(CO 2 Me)dC(CO 2 Me)C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}(µ-Cl)] 2 (6) when R ) CO 2 Me. By reaction of 6 with L (1:2) or PPh 3 and Tl(CF 3 SO 3 ) (1:4:2), the complexes [Pd{C(CO 2 Me)dC(CO 2 Me)C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}Cl(L)] (L ) PPh 3 (7), CNXy (8) (Xy ) 2,6-dimethylphenyl)) or [Pd{C(CO 2 Me)dC(CO 2 Me)C 6 H{C(O)-NHBu t }-6-(OMe) 3 -2,3,4}(PPh 3 ) 2 ](CF 3 SO 3 ) (9) are obtained respectively. The reactions of 4 and of the related complexes [Pd{C 6 H{C(O)Me}-6-(OMe) 3 -2,3,4}(bpy)](CF 3 SO 3 ) (10) or [Pd-{C 6 H{C(O)H}-6-(OMe) 3 -2,3,4}(NCMe)(bpy)](CF 3 SO 3 ) (11) with CNXy have also been studied, the following compounds being isolated: [Pd{C(dNXy)C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}-(bpy)](CF 3 SO 3 ) (12) [Pd{C 6 H{C(O)Me}-6-(OMe) 3 -2,3,4}(CNXy)(bpy)](CF 3 SO 3 ) (13), [Pd-{C 6 H{C(O)H}-6-(OMe) 3 -2,3,4}(CNXy)(bpy)](CF 3 SO 3 ) (14), and the ketenimine 2-(2,6dimethylphenyl)-1-(((2,6-dimethylphenyl)imino)methylene)-5,6,7-trimethoxy-3-oxoisoindoline (15). The structures of 4, 7, 12, and 15 have been determined by X-ray crystallography.

Au(I) trifluoromethyl complexes [Au(CF3)L] (L = N-heterocyclic carbene (NHC), isonitrile, phosphine, P(OMe)3) and [Au2(CF3)2­(μ-dppe)] are prepared by reaction of [Au(X)L] (X = Cl, I) or [Au2Cl2­(μ-dppe)], respectively, with AgF and Me3SiCF3. The analogous reaction of PPN[Au(C6F5)­Cl] (PPN+ = [Ph3PNPPh3]+) gives a mixture of complexes of the type PPN[Au(CF3) x ­(C6F5)2–x ] (x = 0, 1, 2). Single crystals of the new complex PPN[Au(CF3)­(C6F5)] are obtained by liquid diffusion from this mixture, and its crystal structure was determined by X-ray diffraction. Acyclic diaminocarbene complexes [Au(CF3)­{C(NEt2)­(NHR)}] (R = t Bu, 2,6-dimethyl­phenyl) are obtained by reaction of [Au(CF3)­(CNR)] with NHEt2. Oxidation of the NHC complex [Au(CF3)­(IPr)] (IPr = 1,3-bis(2,6-diiso­propyl­phenyl)­imidazol-2-ylidene) with PhICl2, Br2, I2 or ICl affords [Au(CF3)(X)­(Y)(IPr)] (X = Y = Cl, Br I; X = Cl, Y = I). The dicloro, dibromo, and chloro(iodo) complexes are stable in solution in the dark. In contrast, the diiodo complex is unstable and decomposes to [AuI(IPr)] and ICF3. Under photoirradiation, complexes [Au(CF3)(X)­(Y)(IPr)] undergo reductive elimination to give YCF3 and [AuX(IPr)] (X = Y = Cl, Br; X = Cl, Y = I).