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.     

Perhalophenyl complexes of palladium(II) containing keto-stabilized phosphorus ylides of the type Ph2P(CH2)nPPh2CHC(O)R

From suitable perhalophenyl derivatives of palladium(II), viz.: Pd(C₆F₅)₂-(SC₄H₈)₂, [Pd(μ-X′) (C₆X₅)₂]₂(NBu₄)₂, [Pd(μ-Cl)(C₆X₅)(SC₄H₈)]₂ (X = F, Cl, X′ = Cl, Br), new complexes of various types have been prepared, viz.: trans-Pd(C₆F₅)₂(Y)₂, Pd(C₆X₅)₂(Y), PdCl(C₆X₅)(Y) (X = F, Cl). The neutral ligand Y is a keto-stabilized phosphorus ylide of the type Ph₂P(CH₂)_nPPh₂CHC(O)R (n = 1, R = CH₃, C₆H₅; n = 2, R = C₆H₅) acting in a terminal monodentate P-donor or a bidentate chelate P,C-donor mode. The reaction of PdCl(C₆F₅)(Y) complexes with HCl leads to the corresponding PdCl₂(C₆F₅)(YH) complexes in which the phosphonium cation [YH]⁺ behaves as monodentate P-donor at its phosphinic end.IR and ³¹P NMR spectroscopy were used to decide the coordination mode of the ligands and, in some cases, to reveal the presence of two isomers.     

Cationic palladium(II) complexes involving unprecedented O-coordination of acetylmethylenetriphenylphosphorane

Cationic pentafluorophenyl palladium(II) complexes of the type [Pd(C₆F₅)L₂(APPY)]ClO₄ (L = PPh₃, PBu₃ⁿ; L₂ = bipy and A acetylmethylenetriphenylphosphorane) have been prepared by addition of APPY to the perchlorato complexes [Pd(OClO₃)(C₆F₅)L₂]; the APPY ligand is O-coordinated, which is unprecedented in keto-stabilized ylide complexes of palladium.The neutral complex Pd(C₆F₅)(Cl)(tht)(APPY) has been made by addition of APPY to the binuclear complex Pd₂(μ-Cl)₂(C₆F₅)₂(tht)₂ (tht = tetrahydrothiophene); in which the APPY ligand shows the normal C-coordination.     

Pentafluorothiophenolate derivatives of cobalt(II) and nickel(II). The molecular structure of [Ni(SC6F5)2Ph2PCH2CH2PPh2]

Summary The tetrahedral compounds [Co(SC₆F₅)₂L] (L=Ph₂P(CH₂) _n PPh₂,n=1, 2 and 3) and the squareplanar compound [Ni(SC₆F₅)₂(PhPCH₂CH₂PPh₂)] have been obtained by mathematical reactions of [MX₂L] (M=Co or Ni, X=Cl or Br) and Pb(SC₆F₅)₂. The reaction of pentacoordinate [CoCl(Ph₂PCH₂CH₂PPh₂)₂]⁺ and the lead salt yields [CoCl₂L] and [Co(SC₆F₅)₂L]. Magnetic moments, u.v. data (both in solution and solid state) and the crystal and molecular structure of the nickel compound are reported.     

Vinylidene transition-metal complexes: I. Novel rhodium(I) and rhodium(III) complexes containing alkynes,alkynyls, and vinylidenes as ligands.Crystal structure of IC5H5Rh(CCHPh)(PPri3)

The syntheses of the novel cyclopentadienylphosphinevinylidenerhodium complexes C₅H₅Rh(CCHR)(PPrⁱ₃) (R = Ph, Me, H) and, for R = Ph, of the isomeric alkynyl hydrido compound C₅H₅ RhH(C₂Ph)(PPrⁱ₃) are reported. The square-planar complexes trans-[RhCl(RC₂H)(PPrⁱ₃)₂] (IIa, IIb), which in solution are in equi-librium with the five-coordinated pyridine to give the octahedral compounds RhHCl(C₂R)(PRrⁱ₃)₂(py) (VIa, VIb). Treatment of Via, VIb with NaC₅H₅ gives the vinylidene complexes IVa, IVb in good yield. C₅H₅Rh(CCH₂)(PPrⁱ₃) (IVc) is directly obtained from trans-[RhCl(C₂H₂)(PPrⁱ₃)₂] (IIc) and NaC₅H₅. Mechanistic studies confirm that the reaction of VIa, VIb with the cyclopentadienide anion primarily gives, by elimination of HCl, the rhodium(I) compounds trans-[Rh(C₂R)(py)(PPrⁱ₃)₂] (VIIIa, VIIIb), which react with cyclopentadiene, possibly via trans-[Rh(C₂R)(η²-C₅H₆)(PPrⁱ₃)₂](X) as an intermediate, to give C₅ VIIIa with cyclopentadiene in presence of water gives the complex C₅H₅RhH(C₂Ph)(PPrⁱ₃), which isomerizes only slowly to form IVa and, therefore, is not an intermediate in the reaction of VIIIa and C₅H₆ to give IVa. The crystal structure of IVa has been determined. The RhCC arrangement is almost linear. The RhC distance is significantly shorter than in carbenerhodium complexes, which, in agreement with ¹³C NMR data and MO calculations, indicates a high degree of multiple bonding.     

Hydroboration of Alkynes with Zwitterionic Ruthenium–Borate Complexes: Novel Vinylborane Complexes

Building upon previous studies on the synthesis of bis(sigma)borate and agostic complexes of ruthenium, the chemistry of nido‐[(Cp*Ru)₂B₃H₉] ( 1 ) with other ligand systems was explored. In this regard, mild thermolysis of nido‐ 1 with 2‐mercaptobenzothiazole (2‐mbzt), 2‐mercaptobenzoxazole (2‐mbzo) and 2‐mercaptobenzimidazole (2‐mbzi) ligands were performed which led to the isolation of bis(sigma)borate complexes [Cp*RuBH₃L] ( 2 a – c ) and β‐agostic complexes [Cp*RuBH₂L₂] ( 3 a – c ; 2 a , 3 a : L=C₇H₄NS₂; 2 b , 3 b : L=C₇H₄NSO; 2 c , 3 c : L=C₇H₅N₂S). Further, the chemistry of these novel complexes towards various diphosphine ligands was investigated. Room temperature treatment of 3 a with [PPh₂(CH₂)_nPPh₂] (n=1–3) yielded [Cp*Ru(PPh₂(CH₂)_nPPh₂)‐BH₂(L₂)] ( 4 a – c ; 4 a : n=1; 4 b : n=2; 4 c : n=3; L=C₇H₄NS₂). Mild thermolysis of 2 a with [PPh₂(CH₂)_nPPh₂] (n=1–3) led to the isolation of [Cp*Ru(PPh₂(CH₂)_nPPh₂)(L)] (L=C₇H₄NS₂ 5 a – c ; 5 a : n=1; 5 b : n=2; 5 c : n=3). Treatment of 4 a with terminal alkynes causes a hydroboration reaction to generate vinylborane complexes [Cp*Ru(R?C?CH₂)BH(L₂)] ( 6 and 7 ; 6 : R=Ph; 7 : R=COOCH₃; L=C₇H₄NS₂). Complexes 6 and 7 can also be viewed as η‐alkene complexes of ruthenium that feature a dative bond to the ruthenium centre from the vinylinic double bond. In addition, DFT computations were performed to shed light on the bonding and electronic structures of the new compounds.     

Reactions of [Pd(C6F5)2(CNR)2] with [PdCl2(NCPh)2]. Insertion of p-MeC6H4NC into Pd-C6F5 bonds

[Pd(C₆F₅)₂(CNR)₂] (R = Cy, Bu^t, p-MeC₆H₄ (p-Tol)) react with [PdCl₂(NCPh)₂] to give [Pd₂(μ-Cl)₂(C₆F₅)₂(CNR)₂]. In refluxing benzene insertion of isocyanide into the C₆F₅Pd bonds occurs only for R = p-Tol, to give a imidoyl bridged polynuclear complex cis-[Pd₂ (μ-Cl)₂[μ-C(C₆F₅) = N(Tol-p)]_2n]. This complex reacts with (a) Tl(acac) to give [Pd₂{μ-C(C₆F₅) = N(Tol-p)}₂(acac)₂]; (b) neutral monodentate ligands to afford dimeric complexes [Pd₂{μ-C(C₆F₅) = N(Tol-p)}₂Cl₂L₂] (L = NMe₃, py, 4-Me-py, SC₄H₈), and (c) isocyanides to give insoluble complexes of the same composition which are thought to be polymeric, [$\text{Pd}$(CNR)Cl{μ-C(C₆F₅) = $\text{N}$(p-Tol)}]_n (R = p-Tol, Me, Bu^t). Thermal decomposition of cis-[Pd₂ (μ-Cl)₂ [μ-C(C₆F₅) = N( p-Tol)]_2n] gives the diazabutadiene species (p-Tol)NC(C₆F₅)C(C₆F₅)N(p-Tol) in high yield.     

Half-sandwich ruthenium complexes of pentafluorobenzenethiolato ligands

A synthetic study of ruthenium complexes containing pentafluorobenzenethiolato ligand is presented. The bis(triphenylphosphine) complex CpRu(PPh₃)₂SC₆F₅ (1) is prepared from CpRu(PPh₃)₂Cl and C₆F₅S⁻ in high yield. This complex is readily reacted with CO gas to give the mixed carbonyl-phosphine complex CpRu(PPh₃)(CO)SC₆F₅ (2) and with NOBF₄ at room temperature to give [CpRu(PPh₃)(NO)SC₆F₅]BF₄ (3). The one-pot reaction of CpRu(PPh₃)₂Cl, dppa ligands, and C₆F₅S⁻ produces CpRu(dppa)SC₆F₅ [dppa = bis(diphenylphosphino)methane: dppm (4); bis(diphenylphosphino)ethane: dppe (5)]. Complexes (1)–(5) have been characterized by spectroscopic techniques (i.r., ¹H-n.m.r., ³¹P-n.m.r.) and by elemental analysis. The X-ray structural analysis of (5) is reported. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Some reactions of copper(I) pentafluorothiophenolate

Copper(I) pentafluorothiophenolate, CuSC₆F₅ reacted with a number of acyl and alkyl halides in either $\text{n}$-hexane or DMF. The products RCH₂SC₆F₅ (R = Me, Ph, C₆F₅S, C₆F₅SCH₂), Ph₂CHSC₆F₅, R₃CSC₆F₅(R =Me, Ph) and RCOSC₆F₅ (R = Me, C₆F₅) have been characterized and their spectra, particularly NMR spectra (H1, C13, F19) have been examined.     

Pentafluorophenylthiolate derivatives of ruthenium(II), rhodium(I) and palladium(II)

Summary The pentafluorophenylthiolate anion [C₆F₅S]^– reacts with chloro-bridged binuclear complexes of Ru^II, Rh^I and Pd^II to give the compounds [(N-N)(PPh₃)₂Ru(SC₆F₅)]₂Cl₂ (1) (N-N = bipyridine), [LRh(SC₆F₅)]_n (L = cycloocta-1,5-diene (2) or norbornadiene (3), n = 2 and L = dicyclopentadiene (4) for which n is probably 4), [(PPh₃)Pd(SC₆F₅)Cl]₂ (5) and (MeS-CHMeCHMeSMe)Pd(SC₆F₅), (6).¹⁹F n.m.r. spectroscopy shows a variable number of isomers depending on the compound considered.     

Reactions of the carbonyl complexes M(CO)3(L)3 (L = py,M = Mo,W; L = NH3, M = Mo) and M(CO)4(2-Mepy)2 (M = Mo,W) with HgX2 (X = Cl,CN, SCN)

The reactions of the substituted Group VI metal carbonyls of the type M(CO)₄(2-Mepy)₂ (M = Mo, w) and M(CO)₃(L)₃ (L = py, M = Mo, W; L = NH₃, M = Mo) with mercuric derivatives HgX₂ (X = Cl, CN, SCN) have given rise to three series of tricarbonyl complexes: M(CO)₃(py)HgCl₂ · 1/2HgCl₂ (M = Mo, W); 2[M(CO)₃(L)]Hg(CN)·nHg(CN)_x (L = py, M = Mo, W, n = $\text{1}\text{2}$, × = 2; L = 2- Mepy, × = 1; M = Mo, n = 3; M = W, n = 1); and [M(CO)₃(L)Hg(SCN)₂ · nHg(SCN)₂] (L = py, M = Mo,W, n = 0; L = 2-Mepy, M = Mo, W, n = $\text{1}\text{2}$; L = NH₃, M = Mo, n = 0) depending on which mercuric compound is employed. All the reactions with Hg(SCN)₂ give isolable products whereas those with Hg(CN)₂ and HgCl₂ did so far only the reactions with [M(CO)₄(2-Mepy)₂] and M(CO)₃(py)₃. The greater reactivity of Hg(SCN)₂ than of Hg(CN)₂ and HgCl₂ is consistent with the various acceptor capacities of the groups bonded to the mercury atom.The reactions studied always involve displacement of the N-donor ligand of the original complex and partial or total displacement of the halide or pseudohalide groups of the mercury compound to give in all cases compounds containing MHg bonds. In addition, elimination of a CO group in the tetracarbonyl complexes M(CO)₄(2-Mepy)₂occurs.     

Reactions of transition metal σ-acetylide complexes: IX. Preparation and properties of some cycloheptatrienylvinylidene complexes

Addition of [C₇H₇][PF₆] to iron, ruthenium or osmium alkynyl complexes has given eight cationic cycloheptatrienylvinylidene derivatives [M{C C(C₇H₇)R}(L)₂ (η-C₅H₅)][PF₆] (M = Fe, Ru or Os; R = Me, Pr, Ph or C₆F₅; L = PPh₃, L₂ = dppm or dppe; but not all combinations). With Fe(C₂Ph)(CO)₂(η-C₅H₅), only [Fe(CO)₂(thf)(η-C₅H₅)][PF₆] was obtained. Reactions of the new complexes are characterised by loss of the C₇H₇ group. The NMR spectra and FAB mass spectra are described in detail.     

Synthesis and 197Au-Mössbauer spectroscopic studies of dihalo(pentafluorophenyl)(bidentate ligand)gold(III) complexes

Addition of a bidentate ligand (LL = 1,10-phenanthroline, o-phenylenebis(dimethylarsine)) to solutions of Au(C₆F₅)X₂(tht) (X = Cl, Br; tht = tetrahydrothiophene) leads to potentially five-coordinate gold(III) derivatives. ¹⁹⁷Au Mössbauer spectroscopy points, however, to four-coordinate square-planar complexes with a weak penta-coordination in the phen-containing derivatives. The complexes react with AgClO₄ to give four-coordinate cationic complexes of the types [Au(C₅F₅)X(LL)]ClO₄ or [Au(C₆F₅)(PPh₃)(LL)](ClO₄)₂.     

Protonation of the metal—metal bond in Fe2(μ-A)(μ-A′)(CO)4L2 complexes (A  A′ SC6H5, P(C6H5)2, P(CH3)2; A  SC6H5, A′ z.dbnd; P(C6H5)2; L z.dbnd; P(C6H5)3-n(CH3)n). : III. Experimental study of the influence of the A and A′ bridges on the basicity of the metal—metal bond

In order to check the influence of the bridges on the basicity of the metal—metal bond in Fe₂(μ-A)(μ-A′)(CO)₄L₂ complexes, the compounds with A  A′ SC₆H₅, P(C₆H₅)₂; P(CH₃)₂; A  SC₅H₅, A′ P(C₆H₅)₂ and L  P(CH₃)_3-n (C₆H₅)_n (n  0—3) have been prepared. IR and PMR spectroscopic results are interpreted in structural terms, and show that the Fe₂(SC₆H₅)(P(C₆H₅)₂.)-(CO)₄L₂ complexes are non rigid on the NMR time scale for n = 0, 1. Replacement of the first SC₆H₅ bridge by a P(C₆H₅)₂ bridge markedly increase the basicity of the metal—metal bond, but replacement of the second SC₆H₅ bridge has no significant effect.     

Alkyl- und arylverbindungen des vaska'schen typs : IV. cis,trans-Isomerie von iridium-komplexen mit 2,6-dialkylsubstituierten arylliganden

ortho-Substituted aryliridium(I) complexes of the type [Ir(R_nC₆H_5-n)(CO)L₂] (R_nC₆H_5-n = 2-EtC₆H₄; 2,6-Et₂C₆H₃; L = PPh₃ PMePh₂) have been prepared from [IrCl(CO)L₂] and the corresponding aryllithiums. With the exception of trans-[Ir(2-EtC₆H₄)(CO)(PPh₃)₂] these compounds show cis, trans isomerism. After separation, the isomers have been studied by NMR (¹H, ³¹P), IR, and UV-VIS spectroscopy. ab]Durch Umsetzung von [IrCl(CO)L₂] (L = PPh₃, PMePh₂) mit den entsprechenden Lithiumarylen wurden ortho-substituierte Aryliridium(I)-Komplexe des Typs [Ir(R_n C₆H_5-n)(CO)L₂] (R_nC₆H_5?n = 2-EtC₆H₄; 2,6-Et₂C₆H₃; 2-Et-6-MeC₆H₃) dargestellt. Mit Ausnahme von trans-[Ir(2-EtC₆H₄)(CO)(PPh₃)₂] zeigen diese Verbindungen die Erscheinung der cis,trans-Isomerie. Die Isomere wurden getrennt und mit Hilfe NMR- (¹H, ³¹P), IR- und UV/VIS-spektroskopischer Methoden untersucht.     

Decarboxylation syntheses of transition metal organometallics,II.trans-carbonyl(polyhalogenophenyl)bis(triphenylphosphine)rhodium(I) compounds

Summary The rhodium(I) carboxylates,trans-RhO₂CR(CO)(PPh₃)₂ (R = C₆F₅, C₆Cl₅,p-HC₆F₄,m-HC₆F₄,o-HC₆F₄,p-McOC₆F₄, 4,5-H₂C₆F₃, 3,5-H₂C₆F₃, or 2,6-F₂C₆H₃, have been prepared by reaction of RhH(CO)(PPh₃)₃ with the appropriate polyhalogenobenzoic acids in ethanol and/or by reaction oftrans-RhCl(CO)(PPh₃)₂ with the appropriate thallous carboxylates in benzene. Decarboxylations with formation of polyhalogenoarylrhodium(I) compounds,trans-RhR(CO)(PPh₃)₂ (R = C₆F₅, C₆Cl₅,p-HC₆F₄,m-HC₆F₄,p-MeOC₆F₄, 4,5-H₂C₆F₃ or 3,5-H₂C₆F₃), have been achieved either by decomposition of the corresponding rhodium(I) carboxylates in pyridine or by reaction oftrans-RhCl(CO)(PPh₃)₂ and the thallous carboxylates in pyridine, but the derivatives R =o-HC₆F₄ or 2,6-F₂C₆H₃ could not be obtained by this method. The rate of decarboxylation decreased in the sequence R = C₆F₅ >p-MeOC₆F₄ >p-HC₆F₄ >m-HC₆F₄ > 4,5-H₂C₆F₃ > 3,5-H₂C₆F₃.Part 1, ref. 10.Preliminary communication, ref. 9.     

Reactions involving alkynes and tungsten-tungsten triple bonds supported by alkoxide ligands

W₂(OR)₆L_n compounds [R = Bu^t n = 0; R = Prⁱ or Np (Np = neopentyl), L = py (py = pyridine) or HNMe₂, n = 2] react with alkynes (R′C-CR′) under mild conditions (hexane solutions, room temperature or below) to yield a variety of products depending upon the nature of the alkoxide, the alkyne and the mole ratio of the reactants. The products include alkylidyne complexes L_n(RO)₃W CR′ (n = 1 or 0) (Schrock et al., Organometallics 1985, 4, 74), alkyne adducts, W₂(OR)₆(py)_n(μ-C₂R′₂), alkylidyne-capped tritungsten complexes, W₃(μ₃-CR′)(OR)₉, and W₂(OR)₆(L)(μ-C₄R′₄) or W₂(OR)₆(μ-C₄R′₄) (μ²-C₂R′₂) compounds. Evidence for equilibria involving alkyne adducts and alkylidyne species is found for certain combinations of R and R′. (1) The alkylidyne complexes (Bu^tO)₃ WCMe and (py)₂(Pr_iO)₃ W CNMe₂ react with CO (1 atm 22°C, in hexane) to yield alkyne adducts W₂(OBu^t)₆(μ-C₂Me₂)(CO) and W₂[(OPrⁱ)₆(CO)₂(η²-C₂(NMe₂)₂], respectively. (2) The alkylidyne complexes [Pr_iO)₂(HNMe₂)(R′C)W(μ-OPr_i)]₂ react with alkynes R′CCR′ (> 2 equiv, hexane, 22°C) to give W₂(OPr_i)₆(μ-C₄R′₄)(η²-C₂R′₂) compound (R′ = Me or Et). (3) The alkyne adducts W₂(ONp)₆(py)_n(μ-C₂R′₂) (R′ = Et or Ph, n = 1; R′ = Me, n = 2) react with W₂(ONp)₆(py)₂ in a 1:2 mole ratio at 22°C in hexane to yield W₃(μ₃-CR′)(ONp)(₉ compounds. In related reactions involving 1,2-bishydrocarbyl-tetraalkoxides, W₂(CH₂R″)₂(OR)₄, and alkynes (R′CCR′) (2 equiv), alkyne adducts of formula W₂(CH₂R″)₂(η²-C₂R′₂)₂(OPrⁱ)₄ and W₂(CH₃)₂(μ-C₂R′₂)(OBu^t)₄(py), alkylidyne-bridged complexes HW₂(μ-CR″)(μ-C₄R′₄)(OPr_i)₄ and products of WW and CC metathesis have been isolated for various combinations of R, R′ and R″.     

Cluster chemistry: XXXVIII. Reactions between M(C2R)(PR′3 (M = Cu,Ag, Au; R = Ph,C6F5; R′ = Me Ph) and H2Os3(CO)10: X-ray structures of Os3Au(μ-CHCHR)(CO)10(PPh3) (R = Ph and C6F5)

The reactions of Os₃(μ-H)₂(CO)₁₀ with a series of Group IB metal acetylide-tertiary phosphine complexes are described. Whereas the compounds M(C₂C₆F₅)(PPh₃) (M = Cu, Ag, Au) afforded the complexes MOs₃(μ-CHCHC₆F₅)(CO)₁₀(PPh₃) cleanly and in high yield, complex mixtures of products were obtained from reactions of the analogous phenylacetylides. The complexes MOs₃(μ-CHCHPh)(CO)₁₀(PPh₃), MOs₃(μ-CHCHPh)(CO)₉(PPh₃)₂ and MOs₃(μ-H)(CO)₁₀(PPh₃) (of known structure), and MOs₃(μ-CHCHPh)(CO)₉(PPh₃)₂ and HMOs₃(CHCPh)(CO)₈ (of unknown structure) were characterised; Au(C₂Ph)(PMe₃) afforded similar derivatives. The reactions proceed by oxidative-addition and hydrogen migration steps; MP bond cleavage reactions also occur to a small extent. The molecular structures of AuOs₃(μ-CHCHC₆R₅)(CO)₁₀(PPh₃) (R = F or H) were determined by X-ray analyses. For R = F, crystals are triclinic, space group P$\text{1}$ with a 9.081(2), b 13.291(2), c 17.419(2) Å, α 84.49(1), β 76.20(2), γ 75.81(2)° and Z = 2; 4622 observed data [I > 2.5σ(I)] were refined to R = 0.027, R_W = 0.031. For R = H, crystals are triclinic, space group P$\text{1}$, with a 9.403(4), b 13.448(3), c 13.774(4) Å, α 83.34(2), β 88.66(3), γ 70.21(3)°, and Z = 2; 4405 observed data [I > 2.5σ(I)] were refined to R = 0.030, R_W = 0.033. The two molecules differ in the orientation of the Ph rings of the PPh₃ groups, but are otherwise similar to Os₃(μ-H)(μ-CHCHBu^t)(CO)₁₀ with the μ-H ligand replaced by the isolobal μ-Au(PPh₃) group.     

The preparation and X-ray crystal structure of [Ru(SC6F52{P(C6H5)2(H4C6H-2)}2]

The complex [Ru(SC₆F₅)₂(PPh₃)₂] has been prepared from [RuCl₂(PPh₃)₃] and [Pb(SC₆F₅)₂] and shown by X-rays to have a pseudo-octahedral structure apparently with two RuHC interactions. It reacts with CO to give [Ru(SC₆F₅)₂-(CO)₂(PPh₃)₂].     

Polynuclear palladium and gold perhalophenyl derivatives with dppm bridges. Crystal and molecular structure of trans-C6F5Au(μ-dppm)Pd(C6F5)2(μ-dppm)AuC6F5 (dppm = Ph2PCH2PPh2)

Reactions of PdRR′(η¹-dppm)₂ (R = R′= C₆F₅ or C₆Cl₅; R = C₆F₅, R′= Cl; dppm = Ph₂PCH₂PPh₂) with the gold derivatives ClAu(tht), C₆F₅Au(tht), (C₆F₅)₃Au(tht) or O₃ClOAuPPh₃ (tht = tetrahydrothiophen) in appropriate ratios yield the bi- or tri-nuclear complexes PdRR′(dppm)₂AuCl, PdRR′(dppm)₂Au(C₆F₅); PdRR′(dppm)₂Au(C₆F₅)₃; PdRR′(dppmAuCl)₂; PdRR′(dppmAuC₆F₅)₂; PdRR′[dppmAu(C₆F₅)₃]₂, [PdRR′(dppm)₂Au]X (X = ClO₄ or BPh₄); [PPh₃Au(dppm)Pd(C₆F₅)₂(dppm)AuCl]ClO₄ or [PPh₃ Au(dppm)Pd(C₆F₅)₂(dppm)Au(C₆F₅)₃]ClO₄. The structure of trans-Pd(C₆F₅)₂[dppmAu(C₆F₅)]₂ has been determined by X-ray diffraction.