Gold Complexes with Difunctional Perfluoroalkyl Chains: Quantifying the Energy of Aurophilic Interactions in Flexible Open-Chain Complexes

The first binuclear Au^I compounds containing bridging (CF₂)_n chains (n=4, 6, 8) and Au^III metallaperfluorocyclopentanes have been obtained by photoinitiated reactions of LAuMe (L=PPh₃, PMe₃, PCy₃, or IPr) with α,ω-diiodoperfluorocarbons. Complexes LAu(CF₂)₄AuL present an unusual looped structure stabilized by an aurophilic interaction for L=PMe₃, PPh₃, and PCy₃. The study of their dynamic behaviour has provided new insights about the strength of aurophilic interactions in solution, allowing quantification of the energy of a single Au⋅⋅⋅Au interaction.     

Gold Complexes with Difunctional Perfluoroalkyl Chains: Quantifying the Energy of Aurophilic Interactions in Flexible Open‐Chain Complexes

The first binuclear Au^I compounds containing bridging (CF₂)_n chains (n=4, 6, 8) and Au^III metallaperfluorocyclopentanes have been obtained by photoinitiated reactions of LAuMe (L=PPh₃, PMe₃, PCy₃, or IPr) with α,ω‐diiodoperfluorocarbons. Complexes LAu(CF₂)₄AuL present an unusual looped structure stabilized by an aurophilic interaction for L=PMe₃, PPh₃, and PCy₃. The study of their dynamic behaviour has provided new insights about the strength of aurophilic interactions in solution, allowing quantification of the energy of a single Au???Au interaction.     

Preparation and Reactivity of Mixed‐Ligands Hydride Complexes [RuHCl(CO)(PPh3)2{P(OR)3}]

Mixed‐ligands hydride complexes [RuHCl(CO)(PPh₃)₂{P(OR)₃}] ( 2 ) (R = Me, Et) were prepared by allowing [RuHCl(CO)(PPh₃)₃] ( 1 ) to react with an excess of phosphites P(OR)₃ in refluxing benzene. Treatment of hydrides 2 first with triflic acid and next with an excess of hydrazine afforded hydrazine complexes [RuCl(CO)(κ¹‐NH₂NHR1)(PPh₃)₂{P(OR)₃}]BPh₄ ( 3 , 4 ) (R1 = H, CH₃). Diethylcyanamide derivatives [RuCl(CO)(N≡CNEt₂)(PPh₃)₂{P(OR)₃}]BPh₄ ( 5 ) were also prepared by reacting 2 first with HOTf and then with N≡CNEt₂. The complexes were characterized spectroscopically and by X‐ray crystal structure determination of [RuHCl(CO)(PPh₃)₂{P(OEt)₃}] ( 2b ).     

Trinuclear Gold(I) Complexes with Various Coordination Modes of N,N-dimethyldithiocarbamate

The compounds [Au₃(S₂CNMe₂)₃{ ₃-(PPh₂)₃CH]} (1) and [Au₃(S₂CNMe₂)(-S₂CNMe₂){ ₃-(PPh₂)₃CH}]ClO₄ (2) are obtained by reaction of [Au₃Cl₃{ ₃-(PPh₂)₃CH}] with three equivalents of sodium dimethyldithiocarbamate or two equivalents of the same reagent in the presence of excess NaClO₄. Reaction of 2 with the group 11 metal complexes [AuCl(tht)], CuCl or [Au(C₆F₅)(tht)] takes place with displacement of [M(S₂CNMe₂)]_n (M=Cu, Au) and formation of the new complexes [Au₃X(-S₂CNMe₂){ ₃-(PPh₂)₃CH}]ClO₄ (X=Cl (3), X=C₆F₅ (4)); further reaction of 3 with [Ag(OClO₃)(tht)] (tht=tetrahydrothiophene) affords the dicationic species [Au₃(-S₂CNMe₂){ ₃-(PPh₂)₃CH}(tht)](ClO₄)₂ (5). Treatment of [Au₃Cl₃{ ₃-(PPh₂)₃CH}] with one equivalent of NaS₂CNMe₂ allows the substitution of only one chlorine atom, giving rise to the complex [Au₃Cl₂(S₂CNMe₂){ ₃-(PPh₂)₃CH}] (6), in which the dithiocarbamate ligand acts as monodentate rather than bidentate bridging as observed in compounds 3–5. The crystal structures of complexes 1 and 2 have been established by X-ray diffraction studies and show close gold–gold contacts.     

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Trifluoromethylation of AuCl₃ by using the Me₃SiCF₃/CsF system in THF and in the presence of [PPh₄]Br proceeds with partial reduction, yielding a mixture of [PPh₄][Au^I(CF₃)₂] ( 1′ ) and [PPh₄][Au^III(CF₃)₄] ( 2′ ) that can be adequately separated. An efficient method for the high‐yield synthesis of 1′ is also described. The molecular geometries of the homoleptic anions [Au^I(CF₃)₂]^? and [Au^III(CF₃)₄]^? in their salts 1′ and [NBu₄][Au^III(CF₃)₄] ( 2 ) have been established by X‐ray diffraction methods. Compound 1′ oxidatively adds halogens, X₂, furnishing [PPh₄][Au^III(CF₃)₂X₂] (X=Cl ( 3 ), Br ( 4 ), I ( 5 )), which are assigned a trans stereochemistry. Attempts to activate C? F bonds in the gold(III) derivative 2′ by reaction with Lewis acids under different conditions either failed or only gave complex mixtures. On the other hand, treatment of the gold(I) derivative 1′ with BF₃?OEt₂ under mild conditions cleanly afforded the carbonyl derivative [Au^I(CF₃)(CO)] ( 6 ), which can be isolated as an extremely moisture‐sensitive light yellow crystalline solid. In the solid state, each linear F₃C‐Au‐CO molecule weakly interacts with three symmetry‐related neighbors yielding an extended 3D network of aurophilic interactions (Au???Au=345.9(1) pm). The high $\tilde \nu $ _CO value (2194 cm^?1 in the solid state and 2180 cm^?1 in CH₂Cl₂ solution) denotes that CO is acting as a mainly σ‐donor ligand and confirms the role of the CF₃ group as an electron‐withdrawing ligand in organometallic chemistry. Compound 6 can be considered as a convenient synthon of the “Au^I(CF₃)” fragment, as it reacts with a number of neutral ligands L, giving rise to the corresponding [Au^I(CF₃)(L)] compounds (L=CNtBu ( 7 ), NCMe ( 8 ), py ( 9 ), tht ( 10 )).     

Hexanuclear Gold(I) Phosphide Complexes as Platforms for Multiple Redox‐Active Ferrocenyl Units

The synthesis, X‐ray crystal structures, electrochemical, and spectroscopic studies of a series of hexanuclear gold(I) μ₃‐ferrocenylmethylphosphido complexes stabilized by bridging phosphine ligands, [Au₆(P?P)_n(Fc‐CH₂‐P)₂][PF₆]₂ (n=3, P?P=dppm (bis(diphenylphosphino)methane) ( 1 ), dppe (1,2‐bis(diphenylphosphino)ethane) ( 2 ), dppp (1,3‐bis(diphenylphosphino)propane) ( 3 ), Ph₂PN(C₃H₇)‐PPh₂ ( 4 ), Ph₂PN(Ph‐CH₃‐p)PPh₂ ( 5 ), dppf (1,1′‐bis(diphenylphosphino)ferrocene) ( 6 ); n=2, P?P=dpepp (bis(2‐diphenylphosphinoethyl)phenylphosphine) ( 7 )), as platforms for multiple redox‐active ferrocenyl units, are reported. The investigation of the structural changes of the clusters has been probed by introducing different bridging phosphine ligands. This class of gold(I) μ₃‐ferrocenylmethylphosphido complexes has been found to exhibit one reversible oxidation couple, suggestive of the absence of electronic communication between the ferrocene units through the Au₆P₂ cluster core, providing an understanding of the electronic properties of the hexanuclear Au^I cluster linkage. The present complexes also serve as an ideal system for the design of multi‐electron reservoir and molecular battery systems.     

Syntheses and Structural Studies of Several Diynyl‐Ruthenium Complexes and their Adducts with Cyano‐Alkenes

Herein are described some continuing investigations into the reactions of cyano‐alkenes with diynyl‐ruthenium complexes which have resulted in the preparation and characterisation of diynyl‐ruthenium compounds Ru(C≡CC≡CR)(PP)Cp [R = Ph, PP = dppe; R = Fc, PP = dppf; R = CPh=CBr₂, PP = (PPh₃)₂], together with the polycyanobutadienyls Ru{C≡CC[=C(CN)₂]CR=CR′(CN)}(PP)Cp′ [R = Fc, (PP)Cp′ = (dppf)Cp; R = H, SiMe₃, (PP)Cp′ = (dppe)Cp*] formed by [2 + 2]‐cycloaddition of the cyano‐alkenes to the outer C≡C triple bonds and subsequent ring‐opening reactions. Single‐crystal XRD molecular structure determinations of six complexes are reported.     

Efficient Blue Phosphorescence in Gold(I)-Acetylide Functionalized Coinage Metal Bis(amidinate) Complexes

The synthesis of linear symmetric ethynyl- and acetylide-amidinates of the coinage metals is presented. Starting with the desilylation of the complexes [{Me₃SiC≡CC(NDipp)₂}₂M₂] (Dipp=2,6-diisopropylphenyl) (M=Cu, Au) it is demonstrated that this compound class is suitable to serve as a versatile metalloligand. Deprotonation with n-butyllithium and subsequent salt metathesis reactions yield symmetric tetranuclear gold(I) acetylide complexes of the form [{(PPh₃)AuC≡CC(NDipp)₂}₂M₂] (M=Cu, Au). The corresponding Ag complex [{(PPh₃)AuC≡CC(NDipp)₂}₂Ag₂] was obtained by a different route via metal rearrangement. All compounds show bright blue or blue-green microsecond long phosphorescence in the solid state, hence their photophysical properties were thoroughly investigated in a temperature range of 20–295 K. Emission quantum yields of up to 41 % at room temperature were determined. Furthermore, similar emissions with quantum yields of 15 % were observed for the two most brightly luminescent complexes in thf solution.     

Further Evidence for ‘Extended’ Cumulene Complexes: Derivatives from Reactions with Halide Anions and Water

Reactions of [Ru{C=C(H)-1,4-C₆H₄C≡CH}(PPh₃)₂Cp]BF₄ ([ 1 a ]BF₄) with hydrohalic acids, HX, results in the formation of [Ru{C≡C-1,4-C₆H₄-C(X)=CH₂}(PPh₃)₂Cp] [X=Cl ( 2 a-Cl ), Br ( 2 a-Br )], arising from facile Markovnikov addition of halide anions to the putative quinoidal cumulene cation [Ru(=C=C=C₆H₄=C=CH₂)(PPh₃)₂Cp]⁺. Similarly, [M{C=C(H)-1,4-C₆H₄-C≡CH}(LL)Cp ]BF₄ [M(LL)Cp’=Ru(PPh₃)₂Cp ([ 1 a ]BF₄); Ru(dppe)Cp* ([ 1 b ]BF₄); Fe(dppe)Cp ([ 1 c ]BF₄); Fe(dppe)Cp* ([ 1 d ]BF₄)] react with H⁺/H₂O to give the acyl-functionalised phenylacetylide complexes [M{C≡C-1,4-C₆H₄-C(=O)CH₃}(LL)Cp’] ( 3 a – d ) after workup. The Markovnikov addition of the nucleophile to the remote alkyne in the cations [ 1 a–d ]⁺ is difficult to rationalise from the vinylidene form of the precursor and is much more satisfactorily explained from initial isomerisation to the quinoidal cumulene complexes [M(=C=C=C₆H₄=C=CH₂)(LL)Cp’]⁺ prior to attack at the more exposed, remote quaternary carbon. Thus, whilst representative acetylide complexes [Ru(C≡C-1,4-C₆H₄-C≡CH)(PPh₃)₂Cp] ( 4 a ) and [Ru(C≡C-1,4-C₆H₄-C≡CH)(dppe)Cp*] ( 4 b ) reacted with the relatively small electrophiles [CN]⁺ and [C₇H₇]⁺ at the β-carbon to give the expected vinylidene complexes, the bulky trityl ([CPh₃]⁺) electrophile reacted with [M(C≡C-1,4-C₆H₄-C≡CH)(LL)Cp’] [M(LL)Cp’=Ru(PPh₃)₂Cp ( 4 a ); Ru(dppe)Cp* ( 4 b ); Fe(dppe)Cp ( 4 c ); Fe(dppe)Cp* ( 4 d )] at the more exposed remote end of the carbon-rich ligand to give the putative quinoidal cumulene complexes [M{C=C=C₆H₄=C=C(H)CPh₃}(LL)Cp’]⁺, which were isolated as the water adducts [M{C≡C-1,4-C₆H₄-C(=O)CH₂CPh₃}(LL)Cp’] ( 6 a–d ). Evincing the scope of the formation of such extended cumulenes from ethynyl-substituted arylvinylene precursors, the rather reactive half-sandwich (5-ethynyl-2-thienyl)vinylidene complexes [M{C=C(H)-2,5-^cC₄H₂S-C≡CH}(LL)Cp’]BF₄ ([ 7 a – d ]BF₄ add water readily to give [M{C≡C-2,5-^cC₄H₂S-C(=O)CH₃}(LL)Cp’] ( 8 a – d )].     

Aryl- and acetylene-nickel(I) complexes

Reduction of various pentafluorophenylnickel(II) complexes in the presence of phosphines gives unstable nickel(I) compounds but Ni(C₆F₅)(CO)₂(PPh₃)₂ is isolated in the presence of CO. Similar NiR(CO)₂(PPh₃)₂ (R = C₆F₅,C₆Cl₅, 2,3,5,6-C₆Cl₄H) are obtained by reaction of the halogenonickel(I) complex with MgRBr or LiR. Reduction of NiX₂L₂ in the presence of acetylenes gives [NiXL₂]₂(μ-PhCCR) (R = H, X = Cl and R = Ph, X = Cl, Br) when L = P-n-Bu₃ but only NiX(PPh₃)₃ are recovered when L = PPh₃. No reaction with the alkyne is observed for [NiX(PPh₃)₂]_n but [NiCl(PPh₃)]_n reacts with RCCR′ to give paramagnetic NiCl(PPh₃)(CRCR′) (R = Ph, R′= H, COOEt), diamagnetic [NiCl(PPh₃)]₂(μ-PhCCPh) and cyclotrimerization when R = R′ = COOMe. Chemical and structural behaviour of the new nickel(I) complexes is described.     

Polyfluorophenylgold(I) complexes

Neutral polyfluorophenyl complexes of the type RAuL and RAuL-LAuR and anionic complexes of the type [AuR₂]^? (R = 2,3,5,6-C₆F₄H, 2,4,6-C,F₃H₂, 3,6-C₆F₂H₃, 4-C₆ FH₄ or 3-CF₃C,H₄) are obtained by the reaction of ClAuL (L = PPh₃, P(cyclohexyl)₃, AsPh₃ or tetrahydrothiophen; L-L = Ph₂PCH₂PPh₂ or Ph₂PCH₂CH₂PPPh₂) with an organolithium derivative and/or the replacement of the initial ligands L by other mono- or bi-dentate ligands.The outcome of the reaction of [AuR₂]^? with [Au(PCy₃)₂]⁺ (Cy = cyclohexyl), depends on the nature of the ligand R; thus with R = 3,6-C₆,F₂H₃ the product is [Au(PCy₃)₂][AuR₂], while with R = 2,4,6-C₆F₃H₂, the product is [Au(PCy₃)(2,4,6-C₆F₃H₂)].     

(Cycloheptatrienyl)hydridotungsten Complexes

Carbonyl(cycloheptatrienyl)iodo(phosphorus donor)tungstens ([WI(C₇H₇)(CO)L]; L = P(OMe)₃, 1a ; L = P[O(i-Pr)]₃, 1b ; L = PPh₃, 1c ) were prepared from dicarbonyl(cycloheptatrienyl)iodotungsten ([WI(C₇H₇)(CO)₂)] via a carbonyl-substitution process. Similarly, bromocarbonyl(phosphorus donor)(1,2,4,6-tetramethylcycloheptatrienyl)tungstens ([WBr(Me₄C₇H₃)(CO)L]; L = P(OMe)₃, 6a ; L = P[O(i-Pr)]₃, 6b ; L = PPh₃, 6c ) were obtained from the reaction of bromodicarbonyl(1,2,4,6)-tetramethylcycloheptatrienyl)tungsten ([WBr(Me₄C₇H₃)(CO)₂]; 4 ) with L. The reduction of 1a - c , 4 , and 6a , b with sodiumdihydridobis(2-methoxyethoxy)aluminium in toluene led to stable hydrido complexes [WH(R₄C₇H₃)(CO)L] (R = H, L = P(OMe)₃, 2a ; R = H, L = P[O(i-Pr)]₃, 2b ; R = H, L = PPh₃, 2c ; R = Me, L = P(OMe)₃, 7a ; R = Me, L = P[O(i-Pr)]₃, 7b ; R = Me, L = CO, 7d ). Complexes 2a and 7b were characterized by X-ray structure analyses.     

Triple Helicates with Golden Strands: Self‐Assembly of M2Au6 Complexes from Gold(I) Metallaligands and Iron(II), Cobalt(II) or Zinc(II) Cations

Alkynyl gold(I) metallaligands [(AuC≡Cbpyl)₂(μ‐diphosphine)] (bpyl=2,2′‐bipyridin‐5‐yl; diphosphine=Ph₂P(CH₂)_nPPh₂, [n=3 (L^Pr), 4 (L^Bu), 5 (L^Pent), 6 (L^Hex)], dppf (L^Fc), Binap (L^Binap) and Diop (L^Diop)) react with MX₂ (M=Fe, Zn, X=ClO₄; M=Co, X=BF₄) to give triple helicates [M₂(L^R)₃]X₄. These complexes, except those containing the semirigid L^Binap metallaligand, present similar hydrodynamic radii (determined by diffusion NMR spectroscopy measurements) and a similar pattern in the aromatic region of their ¹H NMR spectra, which suggests that in solution they adopt a compact structure where the long and flexible organometallic strands are folded. The diastereoselectivity of the self‐assembly process was studied by using chiral metallaligands, and the absolute configuration of the iron(II) complexes with L^Binap and L^Diop was determined by circular dichroism spectroscopy (CD). Thus, (R)‐L^Binap or (S)‐L^Binap specifically induce the formation of (Δ,Δ)‐[Fe₂((R)‐L^Binap)₃](ClO₄)₄ or (Λ,Λ)‐[Fe₂((S)‐L^Binap)₃](ClO₄)₄, respectively, whereas (R,R)‐ or (S,S)‐L^Diop give mixtures of the ΔΔ‐ and ΛΛ‐diastereomers. The ΔΔ helicate diastereomer is dominant in the reaction of Fe^II with (R,R)‐L^Diop, whereas the ΛΛ isomer predominates in the analogous reaction with (S,S)‐L^Diop. The photophysical properties of the new dinuclear alkynyl complexes and the helicates have been studied. The new metallaligands and the [Zn₂(L^R)₃]⁴⁺ helicates present luminescence from [π→π*] excited states mainly located in the C≡Cbpyl units.     

Heterobimetallic Coinage Metal-Ruthenium Complexes Supported by Anionic N-Heterocyclic Carbenes

The lithium complexes [(WCA-NHC)Li(toluene)] of anionic N-heterocyclic carbenes with a weakly coordinating borate moiety (WCA-NHC, WCA=B(C₆F₅)₃, NHC=IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were used for the preparation of silver(I) or copper(I) WCA-NHC complexes. While the reactions in THF with AgCl or CuCl afforded anionic mono- and dicarbene complexes with solvated lithium counterions [Li(THF)_n]⁺ (n=3, 4), the reactions in toluene proceeded with elimination of LiCl and formation of the neutral phosphine and arene complexes [(WCA-NHC)M(PPh₃)] and [(WCA-NHC)M(η²-toluene)] (M=Ag, Cu). The latter were used for the preparation of chlorido- and iodido-bridged heterobimetallic Ag/Ru and Cu/Ru complexes [(WCA-NHC)M(μ-X)₂Ru(PPh₃)(η⁶-p-cymene)] (M=Ag, Cu, X=Cl; M=Ag, X=I). Surprisingly, these complexes resisted the elimination of CuCl, AgCl, or AgI, precluding WCA-NHC transmetalation.     

Gold(I)-Gold(III)-4,4′-bpy-phosphine complexes: Synthesis and multinuclear NMR study

Silver assisted de-bromination gives [Au₂(dppm/dppe/dppa) (OTf)₂], which on reaction with 4,4′-bpy and gold(I) phosphines in CH₂Cl₂ medium, by the self assembly technique, leads to [(PPh₃)Au(4,4′-bpy)Au(PPh₃)], (1a–1d,2), [{Au₂(dppm/dppe/dppa)}{(4,4-bpy)Au(PPh₃)}₂](NO₃)₄, (3), [{Au₄(dppm/dppe/dppa)₂(4,4-bpy)₂}](OTf)_4, (4), [{(PPh₃)Au^I(4,4′-bpy)}₂Au^III(C₆F₅/Mes)](NO₃)₃, (5) [dppm/dppe/dppa =diphenyl phosphino-methane(a), –ethane(b), ammine(c), C₆F₅/Mes pentafluorophenyl/mesitylene]. The maximum molecular peak of the corresponding molecule is observed in the ESI mass spectrum. Ir spectra of the complexes show –C=C–, –C=N–, as well as phosphine, mesitylene and pentafluorophenyl stretching. The ¹H-NMR spectra as well as ³¹P(¹H)-NMR suggest solution stereochemistry, proton movement and phosphorus proton interaction. Considering all the moities there are a lot of carbon atoms in the molecule reflected by the ¹³C(H)-NMR spectrum. In the ¹H–¹H COSY spectrum of the present complexes and contour peaks in the ¹H–¹³C-HMQC spectrum, assign the solution structure and stereoretentive transformation in each step.     

Bis(diphenylphosphino)methane trimethylphosphine alkyl and η-cyclopentadienyl compounds of rhodium(I); P{H} two dimensional δ/J resolved and Overhauser effect nuclear magnetic resonance spectroscopy

Neutral mononuclear tertiary phosphine rhodium(I) complexes of the formula RhX(PMe₃)(dppm), X = Cl, CH₂SiMe₃, CH₂CMe₃, CH₂CMe₂Ph, η⁵-C₅H₅, DPPM = bis(diphenylphosphino)methane, RhCl(PPh₃)(dppm), RhX(dppm)₂, X = Cl, Me and Rh(η⁵-C₅H₅(dppm) have been synthesised. In Rh(η⁵-C₅H₅)(PMe₃)(dppm), the dppm ligand is unidentate according to ³¹P{¹H} NMR and X-ray data.The ³¹P{¹H} NMR spectral parameters of RhX(PR₃)(dppm) have been determined by a combination of two dimensional δ/J resolved spectroscopy and heteronuclear nuclear Overhauser effect difference spectroscopy (NOEDS) in conjunction with iterative analysis of the one dimensional spectra.     

Predicting Stable Molecular Structures for (RNC)2AuIX Complexes

Calculations have been performed at the MP2 and DFT levels for investigating the reasons for the difficulties in synthesizing bis(isocyanide)gold(I) halide complexes. Three‐coordinated gold(I) complexes of the type (R₃P)₂Au^IX ( 1 ) can be synthesized, whereas the analogous isocyanide complexes (RNC)₂Au^IX ( 2 ) are not experimentally known. The molecular structures of (R₃P)₂Au^IX (X = Cl, Br, and I) and (RNC)₂Au^IX with X = halide, cyanide, nitrite, methylthiolate, and thiocyanate are compared and structural differences are discussed. Calculations of molecular properties elucidate which factors determine the strength of the gold‐ligand interactions in (RNC)₂Au^IX. The linear bonding mode of RNC favors a T‐shaped geometry instead of the planar Y‐shaped trigonal structure of (R₃P)₂Au^IX complexes that have been synthesized. An increased polarity of the Au–X bond in 2 leads to destabilization of the Y‐shaped structure. Chalcogen‐containing ligands or cyanide appear to be good X‐ligand candidates for synthesis of (RNC)₂Au^IX complexes.     

Synthesis and Catalytic Use of Gold(I) Complexes Containing a Hemilabile Phosphanylferrocene Nitrile Donor

Removal of the chloride ligand from [AuCl( 1 ‐κP)] ( 2 ) containing a P‐monodentate 1′‐(diphenylphosphanyl)‐1‐cyanoferrocene ligand ( 1 ), by using silver(I) salts affords cationic complexes of the type [Au( 1 )]X, which exist either as cyclic dimers [Au( 1 )]₂X₂ ( 3 a , X=SbF₆; 3 c , X=NTf₂) or linear coordination polymers [Au( 1 )]_nX_n ( 3 a′ , X=SbF₆; 3 b′ , X=ClO₄), depending on anion X and the isolation procedure. As demonstrated for 3 a′ , the polymers can be readily cleaved by the addition of donors, such as Cl^?, tetrahydrothiophene (tht) or 1 , giving rise to the parent compound 2 , [Au(tht)( 1 ‐κP)][SbF₆] ( 5 a ) or [Au( 1 ‐κP)₂][SbF₆] ( 4 a ), respectively, of which the last two compounds can also be prepared by stepwise replacement of tht in [Au( 1 ‐κP)₂][SbF₆]. The particular combination of a firmly coordinated (phosphane) and a dissociable (nitrile) donor moieties renders complexes 3/3′ attractive for catalysis because they can serve as shelf‐stable precursors of coordinatively unsaturated Au^I fragments, analogous to those that result from the widely used [Au(PR₃)(RCN)]X catalysts. The catalytic properties of the Au‐ 1 complexes were evaluated in model annulation reactions, such as the synthesis of 2,3‐dimethylfuran from (Z)‐3‐methylpent‐2‐en‐4‐yn‐1‐ol and oxidative cyclisation of alkynes with nitriles to produce 2,5‐disubstituted 1,3‐oxazoles. Of the compounds tested ( 2 , 3 a′ , 3 b′ , 3 a , 4 a and 5 a ), the best results were consistently achieved with dimer 3 c , which has good solubility in organic solvents and only one firmly bound donor at the gold atom. This compound was advantageously used in the key steps of annuloline and rosefuran syntheses.     

Chemistry of Ruthenium Polypyridine Complexes: VI. Synthesis and Photochemistry of cis-[Ru(bpy)2(bipy)X]q Complexes

Complexes cis-[Ru(bpy)₂(bipy)(X)] ^{n +} [bpy = 2,2'-bipyridyl, bipy = 4,4'-bipyridyl, X = Br^-, ONO^-, CN^- (n = 1); MeCN, PPh₃ (n = 2), and NO⁺ (n = 3)] were synthesized. Irradiation of acetonitrile solutions of the complexes with X = Cl^-, Br^-, ONO^-, NO₂-, CN^-, NH₃, MeCN, and PPh₃ by visible light results in photosubstitution of 4,4'-bipyridyl by a solvent molecule. The electronic absorption spectra of the complexes were assigned on the basis of quantum-chemical calculations. A correlation was revealed between photolysis quantum yields and charges transferred from ligands X upon their coordination.     

Oxorhenium(V) Complexes with 1,3,4‐Triphenyl‐1,2,4‐triazol‐5‐ylidene

Reactions of the oxorhenium(V) complexes [ReOX₃(PPh₃)₂] (X = Cl, Br) with the N‐heterocyclic carbene (NHC) 1,3,4‐triphenyl‐1,2,4‐triazol‐5‐ylidene (L^Ph) under mild conditions and in the presence of MeOH or water give [ReOX₂(Y)(PPh₃)(L^Ph)] complexes (X = Cl, Br; Y = OMe, OH). Attempted reactions of the carbene precursor 5‐methoxy‐1,3,4‐triphenyl‐4,5‐dihydro‐1H‐1,2,4‐triazole ( 1 ) with [ReOCl₃(PPh₃)₂] or [NBu₄][ReOCl₄] in boiling xylene resulted in protonation of the intermediately formed carbene and decomposition products such as [HL^Ph][ReOCl₄(OPPh₃)], [HL^Ph][ReOCl₄(OH₂)] or [HL^Ph][ReO₄] were isolated. The neutral [ReOX₂(Y)(PPh₃)(HL^Ph)] complexes are purple, airstable solids. The bulky NHC ligands coordinate monodentate and in cis‐position to PPh₃. The relatively long Re–C bond lengths of approximate 2.1Å indicate metal‐carbon single bonds.