AuCl(3)-catalyzed benzannulation: synthesis of naphthyl ketone derivatives from o-alkynylbenzaldehydes with alkynes

The reaction of o-alkynylbenzaldehydes 1 and alkynes 2 in the presence of a catalytic amount of AuCl3 in (CH2Cl)2 at 80 degrees C gave naphthyl ketone products in high yields. The AuCl3-catalyzed formal [4 + 2] benzannulation proceeds most probably through the coordination of the triple bond of 1 to AuCl3, the formation of benzo[c]pyrylium auric ate complex via the nucleophilic addition of the carbonyl oxygen atom, the Diels-Alder addition of alkynes 2 to the auric ate complex, and subsequent bond rearrangement. Similarly, the AuCl3-catalyzed reactions of o-alkynylacetophenone and o-alkynylbenzophenone with phenylacetylene afforded the corresponding naphthyl ketone products in good yields.     

Chiral Lewis acid-catalyzed enantioselective intramolecular carbonyl ene reactions of unsaturated alpha-keto esters

[reaction: see text] Chiral Lewis acid-promoted highly enantioselective intramolecular carbonyl ene reactions of unsaturated alpha-keto esters have been investigated. In the presence of chiral Lewis acids such as [Sc((R,R)-Ph-pybox)](OTf)(3) and [Cu((S,S)-Ph-box)](OTf)(2), several unsaturated alpha-keto esters underwent carbonyl ene reactions in CH(2)Cl(2) at room temperature to give monocyclic products in good yield and excellent enantioselectivity.     

Lewis acid-catalyzed [4 + 2] benzannulation between enynal units and enols or enol ethers: novel synthetic tools for polysubstituted aromatic compounds including indole and benzofuran derivatives

The reaction of enynals 1, including o-(alkynyl)benzaldehydes, and carbonyl compounds 2, such as aldehydes and ketones, in the presence of a catalytic amount of AuBr3 in 1,4-dioxane at 100 degrees C gave the functionalized aromatic compounds 3 in high yields. Similarly, the AuBr3-catalyzed reactions of 1 with acetal compounds 5 afforded the corresponding aromatic compounds 3 in good yields. On the other hand, when the reaction was carried out in the presence of a catalytic amount of Cu(NTf2)2 and 1 equiv of H2O in (CH2Cl)2 at 100 degrees C, the decarbonylated naphthalene products 4 were obtained selectively over 3. Benzofused heteroaromatic compounds, such as indole derivatives 13 and benzofuran derivatives 15, were also synthesized by using the present benzannulation methodology.     

Synthesis and structures of cyclic gold complexes containing diphosphine ligands and luminescent properties of the high nuclearity species

A mixture of cyclic gold(I) complexes [Au(2)(μ-cis-dppen)(2)]X(2) (X = OTf 1, PF(6)3) and [Au(cis-dppen)(2)]X (X = OTf 2, PF(6)4) is obtained from the reaction of [Au(tht)(2)]X (tht = tetrahydrothiophene) with one equivalent of cis-dppen [dppen = 1,2-bis(diphenylphosphino)ethylene]. The analogous reaction with trans-dppen or dppa [dppa = bis(diphenylphosphino)acetylene] affords the cyclic trinuclear [Au(3)(μ-trans-dppen)(3)]X(3) (X = OTf 11, PF(6)12) and tetranuclear [Au(4)(μ-dppa)(4)]X(4) (X = OTf 13, PF(6)14, ClO(4)15) gold complexes, respectively. Recrystallization of 15 from CH(2)Cl(2)/MeOH yielded a crystal of the octanuclear gold cluster [Au(8)Cl(2)(μ-dppa)(4)](ClO(4))(2)16. Attempts to prepare dicationic binuclear gold(II) species from the reaction of a mixture of 3 and 4 with halogens gave a mixture of products, the components of which confirmed to be acyclic binuclear gold(I) [Au(2)X(2)(cis-dppen)] (X = I 5, Br 7) and cyclic mononuclear gold(III) [AuX(2)(cis-dppen)]PF(6) (X = I 6, Br 8) complexes. Complexes 11-14 reveal weak emission in butyronitrile glass at 77 K, but they are non-emissive at room temperature. Ab initio modelling was performed to determine the charge state of the gold atoms involved. Extensive structural comparisons were made to experimental data to benchmark these calculations and rationalize the conformations.     

AuBr3- and Cu(OTf)2-catalyzed intramolecular [4 + 2] cycloaddition of tethered alkynyl and alkenyl enynones and enynals: a new synthetic method for functionalized polycyclic hydrocarbons

[reaction: see text] Treatment of tethered alkynyl enynones 8, in which a carbon chain is attached to the carbonyl group, with a catalytic amount of AuBr(3) in (ClCH(2))(2) gave the naphthyl ketones 9 in good to high yields (top-down approach). Analogously, the AuBr(3)-catalyzed benzannulations of 10, in which a carbon tether is extended from the alkynyl terminus, also proceeded smoothly, and the cyclized naphthyl ketones 11 were obtained in high yields (bottom-up approach). Similarly, when two kinds of tethered alkenyl enynones 12 and 14 were treated with Cu(OTf)(2) catalyst, the corresponding dihydronaphthyl ketone products 13 and 15 were obtained in high yields, respectively. The present formal [4 + 2] intramolecular cycloaddition proceeds most probably through the coordination of the triple bond at the ortho position of substrates to Lewis acids, the formation of benzopyrylium ate complex 16 via the nucleophilic addition of the carbonyl oxygen atom, the reverse electron demand type Diels-Alder addition of the tethered alkynes or alkenes to the ate complex, and subsequent bond rearrangement.     

Gold and silver complexes with the ferrocenyl phosphine FcCH2PPh2

Linear gold(I) and silver(I) complexes with the ferrocenyl phosphine FcCH2PPh2 [Fc = (eta5-C5H5)Fe(eta5-C5H4)] of the types [AuR(PPh2CH2Fc)], [M(PPh3)(PPh2CH2Fc)]OTf, and [M(PPh2CH2Fc)2]OTf (M = Au, Ag) have been obtained. Three-coordinate gold(I) and silver(I) derivatives of the types [AuCl(PPh2CH2Fc)2] and [M(PPh2CH2Fc)3]X (M = Au, X = ClO4; M = Ag, X = OTf) have been obtained from the corresponding gold and silver precursors in the appropriate molar ratio, although some of them are involved in equilibria in solution. The crystal structures of [AuR(PPh2CH2Fc)] (R = Cl, C6F5), [AuL(PPh2CH2Fc)]OTf (L = PPh3, FcCH2PPh2), [Au(C6F5)3(PPh2CH2Fc)], and [Ag(PPh2CH2Fc)3]OTf have been determined by X-ray diffraction studies.     

Stable gold(III) complexes with thiosemicarbazone derivatives

Novel thiosemicarbazonato complexes of gold(III) have been prepared from reactions of [Au(damp-C1,N)Cl2(damp- = 2-(N,N-dimethylaminomethyl)phenyl) or [NBu4][AuCl4] with 2-pyridineformamide thiosemicarbazones (HL). The thiosemicarbazones deprotonate and coordinate as mononegative, tridentate NNS ligands to gold to give [Au(Hdamp-C1)(L)]Cl2 or [AuCl(L)]Cl complexes. The organometallic damp- ligand is protonated during the reactions and the Au-N bond is cleaved. The [AuCl(L)]+ cations represent the first gold(III) complexes with thiourea derivatives which are not stabilised by an additional organometallic ligand. Reactions of [NBu4][AuX4](X = Cl, Br) with diphenylthiocarbazone (dithizone) result in reduction of the metal and the formation of gold(I) complexes of the composition [AuX(SCN4-3,4-Ph2)] where SCN4-3,4-Ph2 is 3,4-diphenyltetrazole thione which is formed from cyclisation of dithizone.     

AuClx (x=1, 3)催化2-炔丙基苯酮与苯炔环化反应机理

对金属元素Au采用LanL2DZ基组,对非金属元素C,H,O,Cl采用6-31G*和6-311++G**基组,用密度泛函理论的B3LYP、B3PW91、UB3LYP方法和二阶微扰理论MP2方法研究了不同氧化态的金催化剂催化2-炔丙基苯酮与苯炔环化反应的机理.结果表明:在AuCl和AuCl3的作用下,反应均能通过[4+2]和[3+2]途径生成产物.但在AuCl催化下,[4+2]反应途径比[3+2]反应途径具有更低的活化自由能,反应主要通过[4+2]途径进行;而在AuCl3催化下,[4+2]反应途径与[3+2]反应途径的活化自由能相近,反应通过两条途径竞争生成产物.比较AuCl和AuCl3的催化效果发现,不同氧化态的金催化剂改变了反应的机理,该反应的活化自由能在AuCl作用下比在AuCl3作用下低11.18 kJ·mol-1.对于该反应,AuCl表现出了更好的催化活性.这些计算结果和实验现象相吻合.     

Substitution reactions of [Ru(dppe)(CO)(H(2)O)(3)][OTf](2)

The labile nature of the coordinated water ligands in the organometallic aqua complex [Ru(dppe)(CO)(H(2)O)(3)][OTf](2) (1) (dppe = Ph(2)PCH(2)CH(2)PPh(2); OTf = OSO(2)CF(3)) has been investigated through substitution reactions with a range of incoming ligands. Dissolution of 1 in acetonitrile or dimethyl sulfoxide results in the facile displacement of all three waters to give [Ru(dppe)(CO)(CH(3)CN)(3)][OTf](2) (2) and [Ru(dppe)(CO)(DMSO)(3)][OTf](2) (3), respectively. Similarly, 1 reacts with Me(3)CNC to afford [Ru(dppe)(CO)(CNCMe(3))(3)][OTf](2) (4). Addition of 1 equiv of 2,2'-bipyridyl (bpy) or 4,4'-dimethyl-2,2'-bipyridyl (Me(2)bpy) to acetone/water solutions of 1 initially yields [Ru(dppe)(CO)(H(2)O)(bpy)][OTf](2) (5a) and [Ru(dppe)(CO)(H(2)O)(Me(2)bpy)][OTf](2) (6a), in which the coordinated water lies trans to CO. Compounds 5a and 6a rapidly rearrange to isomeric species (5b, 6b) in which the ligated water is trans to dppe. Further reactivity has been demonstrated for 6b, which, upon dissolution in CDCl(3), loses water and coordinates a triflate anion to afford [Ru(dppe)(CO)(OTf)(Me(2)bpy)][OTf] (7). Reaction of 1 with CH(3)CH(2)CH(2)SH gives the dinuclear bridging thiolate complex [[(dppe)Ru(CO)](2)(mu-SCH(2)CH(2)CH(3))(3)][OTf] (8). The reaction of 1 with CO in acetone/water is slow and yields the cationic hydride complex [Ru(dppe)(CO)(3)H][OTf] (9) via a water gas shift reaction. Moreover, the same mechanism can also be used to account for the previously reported synthesis of 1 upon reaction of Ru(dppe)(CO)(2)(OTf)(2) with water (Organometallics 1999, 18, 4068).     

Mononuclear and dinuclear complexes with a [Ru(tBu2PCH2CH2PtBu2)(CO)] core

Thermolysis of solid [Ru(d(t)bpe)(CO)2Cl2](2, d(t)bpe =(t)Bu2PCH2CH2P(t)Bu2) under vacuum affords the five-coordinate complex [Ru(d(t)bpe)(CO)Cl2] (4), which was shown by X-ray crystallography to contain a weak remote agostic interaction. In solution, 4 can be readily trapped by CO, CH3CN or water to give [Ru(d(t)bpe)(CO)(L)Cl2](L = CO, 2; L = CH3CN, 6; L = H2O, 7). Reaction of 4 with AgOTf/H2O yields the tris-aqua complex [Ru(d(t)bpe)(CO)(H2O)3](OTf)2 (8), which has been structurally characterised and probed in solution by pulsed-gradient spin echo (PGSE) NMR spectroscopy. The water ligands in 8 are labile and easily substituted to give [Ru(d(t)bpe)(CO)(NCCH3)3](OTf)2 (10) and [Ru(d(t)bpe)(CO)(DMSO)3](OTf)2 (11). In the presence of CO, the tris-aqua complex undergoes water-gas shift chemistry with formation of the cationic hydride species [Ru(d(t)bpe)(CO)3H](OTf) (12) and CO2. X-Ray crystal structures of complexes 2, 4, 6, 8 and 11-12 are reported along with those for [{Ru(d(t)bpe)(CO)}2(mu-Cl)2(mu-OTf)](OTf) (3), [{Ru(d(t)bpe)(CO)}2(mu-Cl)3][Ru(d(t)bpe)(CO)Cl3](5) and [Ru(d(t)bpe)(CO)(H2O)2(OTf)](OTf)(9).     

Intra- and inter-molecular phosphoryl migration in phosphinothiazolines; precursors to polynuclear complexes and bimetallic coordination polymers

Two tautomers of the new phosphinoaminothiazoline Ph2PNHC=NCH2CH2S, obtained from the reaction of 2-amino-2-thiazoline (ATHZ) with Ph(2)PCl, have been structurally characterized and the intermediate formation of the diphosphine Ph2PN=CN(PPh2)CH2CH2S has been demonstrated experimentally and by DFT calculations; reacts with [AuCl(THT)] to give [(AuCl)2] whereas the bidentate metalloligand cis-[Pt(1(-H))2] reacts with AgOTf to form the Ag-Pt coordination polymer [Ag(infinity)[Pt(1(-H))2](infinity)](OTf)(infinity).     

Osmabenzenes from the reactions of a dicationic osmabenzyne complex

Treatment of the osmabenzyne Os([triple bond]CC(SiMe(3))=C(Me)C(SiMe(3))=CH)Cl(2)(PPh(3))(2) (1) with 2,2'-bipyridine (bipy) and thallium triflate (TlOTf) produces the thermally stable dicationic osmabenzyne [Os([triple bond]CC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)](OTf)(2) (2). The dicationic osmabenzyne 2 reacts with ROH (R = H, Me) to give osmabenzene complexes [Os(=C(OR)CH=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf, in which the metallabenzene ring deviates significantly from planarity. In contrast, reaction of the dicationic complex 2 with NaBH(4) produces a cyclopentadienyl complex, presumably through the osmabenzene intermediate [Os(=CHC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf. The higher thermal stability of [Os(=C(OR)CH=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf relative to [Os(=CHC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf can be related to the stabilization effect of the OR groups on the metallacycle. A theoretical study shows that conversion of the dicationic osmabenzyne complex [Os([triple bond]CC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)](OTf)(2) to a carbene complex by reductive elimination is thermodynamically unfavorable. The theoretical study also suggests that the nonplanarity of the osmabenzenes [Os(=C(OR)CH=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf is mainly due to electronic reasons.     

Cu（OTf）2催化苄基卤代物与三丁基烯丙基锡的偶联反应

研究了苄基卤代物与三丁基烯丙基锡的偶联反应,当以10mol%Cu(OTf)2为催化剂,CH2Cl2为溶剂时,1-氯甲基-4-苯基萘与三丁基烯丙基锡于室温反应1h,交叉偶联反应产物1-(3-丁烯基)-4-苯基萘(3b)收率即达93%.结果表明,芳环含供电子基的底物反应活性较高,在室温反应几分钟即可完成,而芳环含吸电子基的底物反应活性低.反应产物3b,1-溴-4-(3-丁烯基)萘(3c)和1-(3-丁烯基)-4-硝基萘(3f)未见报道,且其结构经表征确认.     

Electronic and medium effects on the rate of arene C [bond] H activation by cationic Ir(III) complexes

A detailed mechanistic study of arene C [bond] H activation in CH(2)Cl(2) solution by Cp(L)IrMe(X) [L = PMe(3), P(OMe)(3); X = OTf, (CH(2)Cl(2))BAr(f); (BAr(f) = B[3,5-C(6)H(3)(CF(3))(2)](4))(-)] is presented. It was determined that triflate dissociation in Cp(L)IrMe(OTf), to generate tight and/or solvent-separated ion pairs containing a cationic iridium complex, precedes C [bond] H activation. Consistent with the ion-pair hypothesis, the rate of arene activation by Cp(L)IrMe(OTf) is unaffected by added external triflate salts, but the rate is strongly dependent upon the medium. Thus the reactivity of Cp(PMe(3))IrMe(OTf) can be increased by almost 3 orders of magnitude by addition of (n-Hex)(4)NBAr(f), presumably because the added BAr(f) anion exchanges with the OTf anion in the initially formed ion pair, transiently forming a cation/borate ion pair in solution (special salt effect). In contrast, addition of (n-Hex)(4)NBAr(f) to [CpPMe(3)Ir(Me)CH(2)Cl(2)][BAr(f)] does not affect the rate of benzene activation; here there is no initial covalent/ionic pre-equilibrium that can be perturbed with added (n-Hex)(4)NBAr(f). An analysis of the reaction between Cp(PMe(3))IrMe(OTf) and various substituted arenes demonstrated that electron-donating substituents on the arene increase the rate of the C [bond] H activation reaction. The rate of C(6)H(6) activation by [Cp(PMe(3))Ir(Me)CH(2)Cl(2)][BAr(f)] is substantially faster than [Cp(P(OMe)(3))Ir(Me)CH(2)Cl(2)][BAr(f)]. Density functional theory computations suggest that this is due to a less favorable pre-equilibrium for dissociation of the dichloromethane ligand in the trimethyl phosphite complex, rather than to a large electronic effect on the C [bond] H oxidative addition transition state. Because of these combined effects, the overall rate of arene activation is increased by electron-donating substituents on both the substrate and the iridium complex.     

Tri- and tetracoordinate copper(I) complexes bearing bidentate soft/hard SN and SeN ligands based on 2-aminopyridine

The coordination properties of the EN ligands N-(2-pyridinyl)amino-diphenylphosphine sulfide, N-(2-pyridinyl)amino-diisopropylphosphine sulfide, N-(2-pyridinyl)amino-diphenylphosphine selenide, N-(2-pyridinyl)amino-diisopropylphosphine selenide towards copper(I) precursors CuX (X = Br, I), [Cu(IPr)Cl] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), and [Cu(CH(3)CN)(4)]PF(6) were studied. Treatment of CuX with EN ligands resulted in the formation of tricoordinate complexes of the type [Cu(κ(2)(E,N)-EN)X]. The reaction of [Cu(IPr)Cl] with EN ligands, followed by halide abstraction with AgSbF(6), afforded cationic tricoordinate complexes [Cu(κ(2)(S,N)-EN)(IPr)](+), while the reaction of [Cu(CH(3)CN)(4)](+) with two equivalents of EN ligands yielded tetrahedral complexes [Cu(κ(2)(E,N)-EN)(2)](+). Halide removal from [Cu(κ(2)(S,N)-SN)I] with silver salts in the presence of L = CH(3)CN and CNtBu afforded dinuclear complexes of the type [Cu(κ(2)(S,N),μ(S)-SN)(L)](2)(2+) containing bridging SN ligands. With the terminal alkynes HC≡CC(6)H(4)Me and HC≡CC(6)H(4)OMe, complexes of the formula [Cu(κ(2)(S,N)-SN-iPr)(η(2)-HC≡CC(6)H(4)Me)](+) and [Cu(κ(2)(S,N)-SN-iPr)(η(2)-HC≡CC(6)H(4)OMe)](+) were obtained. The mononuclear nature of these compounds was supported by DFT calculations. Most complexes were also characterized by X-ray crystallography.     

The first acetimine gold(I) and gold(III) complexes and the first acetonine complexes

Ketimino(phosphino)gold(I) complexes of the type [Au[NR=C(Me)R']L]X (X = ClO4, R = H, L = PPh3, R'=Me (la), Et (2a); L=PAr3 (Ar=C6H4OMe-4), R'=Me (1b), Et (2b); L=PPh3, R=R'=Me (3); X= CF3SO3 (OTf), L=PPh3, R=R'=Me (3'); R=Ar, R'=Me (4)) have been prepared from [Au(acac)L] (acac = acetyl acetonate) and ammonium salts [RNH3]X dissolved in the appropriate ketone MeC(O)R'. Complexes [Au(NH=CMe2)2]X (X = C1O4 (6), OTf (6')) were obtained from solutions of [Au(NH3)2]X in acetone. The reaction of 6 with PPN[AuCl2] or with PhICl2 gave [AuCl(NH=CMe2)] (7) or [AuCI2(NH=CMe2)2]ClO4 (8), respectively. Complex 7 was oxidized with PhICl2 to give [AuCl3(NH=CMe2)] (9). The reaction of [AuCl(tht)] (tht = tetrahydrothiophene), NaClO4, and ammonia in acetone gave [Au(acetonine)2]ClO4 (10) (acetonine = 2,2,4,4,6-pentamethyl-2,3,4,5-tetrahydropyrimidine) which reacted with PPh3 or with PPN[AuCl2] to give [Au(PPh3)(acetonine)]ClO4 (11) or [AuCl(acetonine)] (12), respectively. Complex 11 reacts with [Au(PPh3)(Me2CO)]ClO4 to give [(AuPPh3)2(mu-acetonine)](ClO4)2 (13). The reaction of AgClO4 with acetonine gave [Ag(acetonine)(OClO3)] (14). The crystal structures of [Au(NH2Ar)(PPh3)]OTf (5), 6' and 10 have been determined.     

AuBr(3)-catalyzed [4 + 2] benzannulation between an enynal unit and enol

The reaction of enynals 1, including o-alkynylbenzaldehydes, and carbonyl compounds 2 in the presence of a catalytic amount of AuBr3 in 1,4-dioxane at 100 degrees C gave the functionalized aromatic compounds 3 in high yields. The AuBr3-catalyzed formal [4 + 2] benzannulation proceeds most probably through the coordination of the triple bond of 1 to AuBr3, the formation of a pyrylium auric ate complex via the nucleophilic addition of the carbonyl oxygen atom, the reverse electron demand-type Diels-Alder addition of the enols, derived from 2, to the auric ate complex, and subsequent dehydration and bond rearrangement. Similarly, the AuBr3-catalyzed reactions of 1 with acetal compounds afforded the corresponding aromatic compounds in good yields.     

Unprecedented luminescent heteropolynuclear aggregates with gold thiolates as building blocks

The reaction of [AuCl(P-N)], in which P-N represents a heterofunctional phosphine ligand, with pentafluorothiophenol, HSC(6)F(5), gives the thiolate gold derivatives [Au(SC(6)F(5))(P-N)] (P-N = PPh(2)py (1), PPh(2)CH(2)CH(2)py (2), or PPhpy(2) (3)). Complex [Au(SC(6)F(5))(PPh(2)py)] (1) reacts with [Au(OTf)(PPh(2)py)] in a 1:1 or 1:2 molar ratio to afford the di- or trinuclear species [Au(2)(μ-SC(6)F(5))(PPh(2)py)(2)]OTf (4) and [Au(3)(μ(3)-SC(6)F(5))(PPh(2)py)(3)](OTf)(2) (5), with the thiolate acting as a doubly or triply bridging ligand. The reactivity of the mononuclear compounds [Au(SC(6)F(5))(P-N)] toward silver or copper salts in different ratios has been investigated. Thus, the treatment of [Au(SC(6)F(5))(P-N)] with Ag(OTf) or [Cu(NCMe)(4)]PF(6) in a 1:1 molar ratio gives complexes of stoichiometry [AuAg(OTf)(μ-SC(6)F(5))(P-N)] (P-N = PPh(2)py (6), PPh(2)CH(2)CH(2)py (7), or PPhpy(2) (8)) or [AuCu(μ-SC(6)F(5))(P-N)(NCMe)]PF(6) (P-N = PPh(2)py (9), PPh(2)CH(2)CH(2)py (10), or PPhpy(2) (11)). These complexes crystallize as dimers and display different coordination modes of the silver or copper center, depending on the present functionalized phosphine ligand. The treatment of [Au(SC(6)F(5))(PPh(2)py)] with silver and copper compounds in other molar ratios has been carried out. In a 2:1 ratio, the complexes [Au(2)M(μ-SC(6)F(5))(2)(μ-PPh(2)py)(2)]X (M = Ag, X = OTf (12); M = Cu, X = PF(6) (13)) are obtained. The same reaction in a 4:3 molar ratio affords the species [Au(4)M(2)(μ-SC(6)F(5))(3)(μ-PPh(2)py)(4)]X(3) (M = Ag, X = OTf (14); M = Cu, X = PF(6) (15)). The crystal structures of some of these complexes reveal different interactions among the metallic d(10) centers. The complexes display dual emission. The band at higher energy has been attributed to intraligand (IL) transitions, and the one at lower energy has been assigned to a ligand to metal (LM) charge transfer process. The latter emission is modulated by the heterometal (silver or copper).     

Water-soluble ruthenium(II) catalysts [RuCl2(eta6-arene)[P(CH2OH)3]] for isomerization of allylic alcohols and alkyne hydration

The novel water-soluble ruthenium(II) complexes [RuCl(2)(eta(6)-arene)[P(CH(2)OH)(3)]]2a-c and [RuCl(eta(6)-arene)[P(CH(2)OH)(3)](2)][Cl]3a-c have been prepared in high yields by reaction of dimers [[Ru(eta(6)-arene)(micro-Cl)Cl](2)](arene = C(6)H(6)1a, p-cymene 1b, C(6)Me(6)1c) with two or four equivalents of P(CH(2)OH)(3), respectively. Complexes 2/3a-c are active catalysts in the redox isomerization of several allylic alcohols into the corresponding saturated carbonyl compounds under water/n-heptane biphasic conditions. Among them, the neutral derivatives [RuCl(2)(eta(6)-C(6)H(6))[P(CH(2)OH)(3)]]2a and [RuCl(2)(eta(6)-p-cymene)[P(CH(2)OH)(3)]]2b show the highest activities (TOF values up to 600 h(-1); TON values up to 782). Complexes 2/3a-c also catalyze the hydration of terminal alkynes.     

Auration, argentation, and mercuration reactions of an iridaphosphirene

The reactions of the iridaphosphirene complex [Ir{=C(tBu)P(Cy)}(CO)(PPh3)2] (Cy = cyclohexyl) with either [AuCl(tht)] (tht = tetrahydrothiophene) or AgCl result in the products [Ir{=C(tBu)P[M(Cl)](Cy)}(CO)(PPh3)2], M = Au or Ag. The aurated product can additionally be obtained on reaction of the iridaphosphirene with [AuCl(CNtBu)], via loss of the isocyanide ligand. Treatment of [Ir{=C(tBu)P(Cy)}(CO)(PPh3)2] with [AuCl(PPh3)] in the presence of silver triflate leads to the isolation of the salt, [Ir{=C(tBu)P[Au(PPh3)](Cy)}(CO)(PPh3)2][SO3CF3]. Reaction of the iridaphosphirene with PhHgCl in the absence or presence of silver triflate affords the mercurated species [Ir{=C(tBu)P[Hg(Ph)](Cy)}(CO)(PPh3)2]X, X = Cl or CF3SO3, respectively. The former exhibits a weakly mercury-coordinated chloride ion. The X-ray crystal structures of all of the complexes are described.