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).

The synthesis of [RhF(COD)] n and its triphenylphosphine adduct 2, and a preliminary study of the reactivity of 2 are reported. The reactivity of the Rh−F bond is illustrated by the reactions that lead to compounds 5 and 6. Compound 5 is the first trifluoromethyl Rh(I) complex characterized by monocrystal X-ray diffraction. Both compounds 2 and 6 are initiators of the polymerization of phenylacetylene.

Compounds trans-[RhF(dCdCHR)(PiPr 3 ) 2 ] (2-4), of which 2 (R ) H) was prepared for the first time from [Rh{η 2 -O 2 S(O)CF 3 }(PiPr 3 ) 2 ], C 2 H 2 , and KF, reacted with Ph 3 SnCtC-CtCSnPh 3 to give the dinuclear C 4 -bridged rhodium(I) complexes trans,trans-[{Rh(dCdCHR)-(PiPr 3 ) 2 } 2 (µ-CtC-CtC)] (5-7) in 78-88% isolated yield. On a similar route, by using trans-[RhF(CX)(PiPr 3 ) 2 ] (8, CX ) CNC 6 H 3 Me 2 -2,6; 9, CX ) CO) and Ph 3 SnCtC-CtCSnPh 3 in the molar ratio of 2:1 as the starting materials, the diisocyanidedirhodium and dicarbonyldirhodium derivatives trans,trans-[{Rh(CX)(PiPr 3 ) 2 } 2 (µ-CtC-CtC)] (12, 13) were obtained. The reactions of 8 and 9 with equimolar amounts of Ph 3 SnCtC-CtCSnPh 3 gave the mononuclear complexes trans-[Rh(CtC-CtCSnPh 3 )(CX)(PiPr 3 ) 2 ] (10, 11), which on further treatment with 8 or 9 afforded the dinuclear compounds 12 and 13, respectively. The C-SnPh 3 bond of 10 could be cleaved both by Al 2 O 3 /H 2 O and trans-[RhF(dCdCHPh)(PiPr 3 ) 2 ] (3) to give the butadiynyl compound trans-[Rh(CtC-CtCH)(CNC 6 H 3 Me 2 -2,6)(PiPr 3 ) 2 ] (14) and the unsymmetrical dirhodium complex trans,trans-[{Rh(dCdCHPh)(PiPr 3 ) 2 }{Rh-(CNC 6 H 3 Me 2 -2,6)(PiPr 3 ) 2 }(µ-CtC-CtC)] (15). Moreover, treatment of 5 and 6 with CNC 6 H 3 -Me 2 -2,6 or CO led to a 2-fold migratory insertion reaction to yield the novel dinuclear compounds trans,trans-[{Rh(CX)(PiPr 3 ) 2 } 2 {µ-C(dCHR)CtC-CtC-C(dCHR)}] (16-18), which contain a highly unsaturated eight-membered C 8 chain as a bridge. The molecular structure of 17 (CX ) CO; R ) Ph) was determined by X-ray crystallography.

The reactions of bis{~2-(2,3,4-trimethoxy-6-acetylphenyl-C,O)}bis~-chloro)dipalladium- (11) (1) with different internal alkynes ArC=CR, Ar = aryl and R = aryl or C02R, result in the selective formation of spirocyclic organic compounds. Thus, 1 reacts with diphenyl-or bis(4-toly1)acetylene giving l0-acetyl-6,7-dimethoxy-1,2,3,4-tetraphenylspiro[4.5]1,3,6,9-decatetraen-&one (2) or l0-acetyl-6,7-dimethoxy-1,2,3,4-tetrakis(4-tolyl)spiro[4.5ll,3,6,9-decatetraen-&one (3), respectively. Among unsymmetrical alkynes, ethyl 2-phenylpropiolate gives the head-to-tail isomer l0-acetyl-2,4-bis(carboxyethyl)-6,7-dimethoxy-l ,&diphenylspiro-[4.5]1,3,6,9-decatetraen-8-one (4) as the only isomer whereas methyl 2-phenylpropiolate gives l0-acetyl-2,4-bis(carboxymethyl)-6,7-dimethoxy-l,3-diphenylspiro[4.511,3,6,9-decatetraen-8-one (5a) as the major isomer and a small amount of a head-to-head or tail-to-tail isomer (5b), the ratio 5d5b being 5/1. When these reactions are carried out with unsymmetrical diarylalkynes, Ar = Ph, R = 4-nitrophenyl or 4-methoxyphenyl, a moderate or no regioselectivity toward the head-to-tail spiro product is observed. The molar ratios of this isomer to the head-to-head and to the tail-to-tail isomers are, respectively, 4/1/1 or 2/1/1. When one of the sustituents is an alkyl group, for example R = Me, the benzofulvene 5,6,7-trimethoxy-3-methyl-2-phenyl-l-methylene-l~-indene (2-PhBzf) (9) is obtained along with the mixture of spiro compounds (head-to-tail (8a)head-to-head or tail-to-tail (8b) = 7/1; 819 = 8/15). Dialkylacetylenes react with 1 giving benzofdvenes (Bzf). Thus, 1 reacts with dimethyl-or tert-butylmethylacetylene giving 2-MeBzf (10) or 2JBuBzf (11). The reaction of 1 with diethylacetylene gives both isomers E-and 2-5,6,7-trimethoxy-3-methyl-2-ethyl-1-ethylidene-lH-indene, OW12 and (2)-12 (2.6/1). In the reaction of 1 with diphenylacetylene, an organopalladium intermediate can be isolated, which reacts with 2,2'-bipyridine and thallium(1) trifluoromethylsulfonate giving the (n-ally1)palladium complex, r3-{ 10-acetyl-6,7,8-trimethoxy-1,2,3,4-tetraphenylspiro[4.511,3,6-decatrien-8-enyl}(2,2'-bipyridine)pa.Uadium-(11) trifluoromethylsulfonate (131, the structure of which has previously been reported. Reduction of 2 with Na[BHJ gives 10-(l-hydroxyethyl)-6,7-dimethoxy-l,2,3,4-tetraphenylspiro[4.5]1,3,6,9-decatetraen-8-one (141, the structure of which has been determined by diffraction at -130 "C. It crystallizes in P212121 with a = 10.635(3) A, b = 13.199(4) A, c = 20.643(7) A and R = 0.063). The structure consists of two ring systems, 2,3,4,5-tetraphenylcyclopenta-2,4-diene and 2,3-dimethoxy-6-(l-hydroxyethyl)-cyclohexa-2,5-dien-4-one, with a common spiro carbon atom.

The rhodium(I) fluoro complexes [RhF(COD)(PR 3 )] (R ) Ph (1a), C 6 H 4 OMe-4 (1b), i-Pr (1d), Cy (1e); COD ) 1,5-cyclooctadiene) react with Me 3 SiR F to afford the rhodium(I) 2c)), of which 2a,c were isolated as pure solids. [Rh-(CF 3 )(NBD)(PPh 3 )] (3) was prepared by reaction of 2a with norbornadiene. The reactions of 2a-c with 2,6-dimethylphenyl isocyanide (XyNC) or t-BuNC, in a 1:2 molar ratio, gave the compounds trans- 4c)). The reactions of 2a-c with an equimolar amount of XyNC gave mixtures containing complexes 4a-c as the major products. The peroxo complexes [Rh(CF 3 )(η 2 -O 2 )(CNXy) 2 (PR 3 )], (R ) Ph (7a), C 6 H 4 OMe-4 (7b)) were isolated by reacting O 2 with 4a,b, respectively. The complexes [Rh(R F )(CNR′) 3 -were obtained by reaction of 2a-c with 3 equiv of XyNC. Formation of [Rh(CF 3 )(PPh 3 )-(CO) 3 ] (9) in the reaction of complex 2a with CO was spectroscopically observed. The crystal structures of complexes 4a, 7a, and 8a have been determined by single-crystal X-ray diffraction studies. The dynamic behavior in solution of the prepared complexes was studied by variable-temperature NMR.