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1.
Abstract

The triply halide-bridged binuclear complexes [Ru2Cl5(CO)(AsPh3)3] (AsPh3 = triphenylarsine), [Ru2Cl5(CO)(PPh3)2(AsPh3)] (PPh3 = triphenylphosphine), [Ru2Cl5(CO)(AsPh3)2(PPh3)], [Ru2 Br5(CO)(PPh3)3], [Ru2Cl5(CO)(P{p-tol}3)2(PPh3)] (P{p-tol}3 = tri-p-tolylphosphine) and [Ru2 Br2Cl3(PPh3)2(AsPh3)] were prepared from the precursor compounds ttt-[RuX2(CO)2(P)2] (X = Cl or Br) and [RuY3(P')2S]·S (Y = Cl or Br; P=PPh3, AsPh3 or P{p- tol}3 and P' = AsPh3 or PPh3; S=DMA or MeOH, where DMA = N,N'-dimethylacetamide). The molecular structures of the binuclear complexes [Ru2Cl5(CO)(AsPh3)3] (P21/c), [Ru2Br5(CO)(PPh3)3] (P21/c) and ttt-[RuCl2(CO)2(PPh3)2] (P1) were determined by X-ray diffraction methods. The complexes are always formed by two Ru atoms bridged through three halide anions, two of which are × type (from the RuII precursor) and the other is Y type (from the rutheniumIII precursor) confirming our previously suggested mechanism for obtaining this class of complexes. The RuII atom is also coordinated to a carbon monoxide molecule and two P ligands from the ttt-starting isomer whereas the RuIII atom is bonded to two non-bridging Y halides and one P' molecule. The presence of RuIII was confirmed by EPR data, a technique that was also useful to suggest the symmetry of the complexes. The absence of intervalence charge-transfer transitions (IT) in the near infrared spectrum confirms that the binuclear complexes have localized valence. The IR spectra of the complexes show; (CO) bands close to 1970 cm?1 and ν(Ru-Cl) or(Ru-Br) bands at about 230–380 cm?1 corresponding to halides at terminal or bridged positions. Two widely separated redox processes, RuII/RuII←RuII/RuIII→RuIII/RuIII, were observed by cyclic voltammetry and differential pulse voltammetry.  相似文献   

2.
Interaction of [Ru(NO)Cl3(PPh3)2] with K[N(R2PS)2] in refluxing N,N-dimethylformamide afforded trans-[Ru(NO)Cl{N(R2PS)2}2] (R = Ph (1), Pri (2)). Reaction of [Ru(NO)Cl3(PPh3)2] with K[N(Ph2PSe)2] led to formation of a mixture of trans-[Ru(NO)Cl{N(Ph2PSe)2}2] (3) and trans-[Ru(NO)Cl{N(Ph2PSe)2}{Ph2P(Se)NPPh2}] (4). Reaction of Ru(NO)Cl3 · xH2O with K[N(Ph2PO)2] afforded cis-[Ru(NO)(Cl){N(Ph2PO)2}2] (5). Treatment of [Rh(NO)Cl2(PPh3)2] with K[N(R2PQ)2] gave Rh(NO){N(R2PQ)2}2] (R = Ph, Q = S (6) or Se (7); R = Pri, Q = S (8) or Se (9)). Protonation of 8 with HBF4 led to formation of trans-[Rh(NO)Cl{HN(Pri2PS)2}2][BF4]2 (10). X-ray diffraction studies revealed that the nitrosyl ligands in 2 and 4 are linear, whereas that in 9 is bent with the Rh–N–O bond angle of 125.7(3)°.  相似文献   

3.
Voltammetric studies reveal that, like [Ru2Cl4(PPh3)4(CO)], triply-bridged complexes [Ru2Cl4L5] (L = PClPh2, PMePh2, PEt2Ph) are reversibly oxidized to [Ru2Cl4L5]+. The mixed valence complexes [Ru2Cl5L3Y] (L = PPh3, P(tol)3; Y = CO, CS) undergo a corresponding reduction to [Ru2Cl5L3Y]?; whereas [Ru2Cl5L4] (L = PEt2Ph, As(tol)3) and [Ru2Cl6(AsPh3)3] are both reduced and oxidised in reversible one-electron steps. For the bridging (RuCl3Ru)z+ moiety, the redox series z = 1, 2, 3, 4 is established.  相似文献   

4.
The complexes [Ru2(CO)2(μ-CO)(μ-CMe)(η-C5H5)2]? and [Ru2CO2(μ-CO)(μ-CCH2)(η-C5H5)2] react together to give [{Ru2CO)3(η-C5H5)2}2(μ-CMeCHCH)]+ and [{Ru3(CO)3(η-C5H5)3}(μ-CCH2CHC){Ru2(CO)3(η-C5H5)2}], each characterised by X-ray diffraction. The former results from ethylidyne-vinylidene linking followed by an alkylidyne to vinyl rearrangement.  相似文献   

5.
Summary Schiff bases (HL) produced by the condensation ofN-methyl-S-methyldithiocarbazate with -diketones and aromatic aldehydes or ketones react with [RuHClCO(PPh3)3] to yield hexacoordinated complexes of the type [RuClCO(PPh3)2(L)]. These Schiff bases react with [RuCl2{P(OR)3}4] in 11 molar ratio to yield [RuCl{P(OR)3}2(L)] in which L is a tridentate. The chlorine atom in the complex can be removed in coordinating solvents in the presence of anions such as [BPh4]– to give cationic complexes. Bis chelate complexes, [Ru{P(OR)3}2(L)2] are prepared from 12 molar proportions of the reactants. These complexes were characterised by elemental analyses, i.r.,1H n.m.r., u.v. and conductivity studies.NCL Communication No. 4224.  相似文献   

6.
The compound [RuCl2(CO)(DMA)(PPh3)2] [DMA = dimethylacetamide] was obtained from [RuCl3(PPh3)2-(DMA)] · DMA and CO in DMA. Orange crystals of [RuCl2(CO)(DMA)(PPh3)2] · 1/2CH2Cl2 were isolated by slow evaporation of a CH2Cl2/DMA solution and its structure was determined by single crystal X-ray diffraction. The analogous compounds containing DMF and DMSO were obtained from the precursor ttt-[RuCl2(CO)2(PPh3)2]. Characterization of the other complexes is based on i.r. and n.m.r. spectroscopy, including 31P{1H} data.  相似文献   

7.
Treatment of Au2(Ph2PCH2CH2PPh2)Cl2 with one equivalent of the [Ru5C(CO)14]2− dianion in the presence of TlPF6 gives Ru5C(CO)14Au2(Ph2PCH2CH2PPh2) (1) in good yield and the [{Ru5C(CO)14}2Au2(Ph2PCH2CH2PPh2)]2− (2) anion in low yield. Complex 2 becomes the major product if 2 equivalents of [Ru5C(CO)14]2− are used. Reaction of [Au2(Ph2PCH2CH2PPh2)Cl2] with 3 equivalents of [H3Os4(CO)12]− anion in the presence of TlPF6 affords {H3Os4(CO)12}2Au2(Ph2PCH2CH2PPh2) (3) in reasonable yield. X-ray diffraction studies of 1 and 3 show that they contain the [Au2(Ph2PCH2CH2PPh2)]2+ fragment in different coordination modes.  相似文献   

8.
The complexes Et4N[Rh(SnCl3)2(diolefin)(PR3)] (diolefin = COD or NBD) have been isolated and their reactions studied. Reaction with arylic tertiary phosphines led to SnCl3− displacement and isolation of neutral pentacoordinated Rh(SnCl3)(diolefin)(PR3)2 complexes. Reaction with carbon monoxide involved diolefin displacement when the diolefin was COD, thus giving Et4N[Rh(SnCl3)2(CO)2(PR3)] compounds, but SnCl3− displacement when it was NBD, thus yielding Rh(SnCl3)(CO)(NBD)(PR3) complexes. The complexes [Rh(diolefin)Cl]2 were found to react with triarylphosphines in the presence of SnCl2 and with CO bubbling through the solution to give Rh(SnCl3)(CO)(NBD)(PR3) when the diolefin was NBD but Rh(Cl)(CO)(PR3)2 when the diolefin was COD.  相似文献   

9.
New anionic carbonylcobalt(I) complexes [X2Co(CO)2(PPh3)](PR4) (X=Cl, PR4 = PBzPh3 (I); X = Br, PR4 = PEtPh3 (II)) have been prepared by reduction of the cobalt(II) halides with NaBH4 in the presence of PPh3 and the phosphonium salt PR4X. Cleavage of halide bridges in dimeric or polymeric [XCo(PPh3)2]n and [XCo(PPh3)]n gives the neutral dicarbonyl derivatives XCo(CO)2PPh3)2. Treatment of ClCo(CO)2(PPh3)2 with alkylating agents gives the known σ- and η- organocobalt(I) derivatives, and reactions with TIClO4 in the presence of various amounts of different mono- and bi-dentate phosphines give the cationic tricarbonyl [Co(CO)3(PPh3)2]+, dicarbonyl [Co(CO)2(PMePh2)3]+ and monocarbonyl [Co(CO)L4]+ complexes (L4 = 4P(OMe)3, 2 dppe and 2dppm). The dppm complex crystallizes in the monoclinic space group P21/c with a 17.895(6), b 10.751(2), c 24.687(4) Å, β 98.92(1)°, and Dcalc 1.35 g cm−3 for Z = 4. A final R value of 0.077 ( Rw = 0.061), based on 2656 observed reflections, was obtained. The cobalt atom exhibits a distorted trigonal bipyramidal geometry. The perchlorate anion is severely disordered or freely rotating.  相似文献   

10.
Treatment of [Ru2(μ-CO)(CO)4{μ-(RO)2PN(Et)P(OR)2}2] (R = Me or Pri), electron-rich derivatives of [Ru2(CO)9], with a twice molar amount of a silver(I) salt in aprotic, weakly co-ordinating solvents such as acetone, acetonitrile or benzonitrile leads to the formation of the solvento species [Ru2(CO)5(solvent)- {μ-(RO)2PN(Et)P(OR)2}2]2+. The structure of the benzonitrile derivative, [Ru2(CO)5(PhCN){μ-(PriO)2PN(Et)P(OPri)2}2](SbF6)2, has been established by X-ray crystallography. The acetone molecule in [Ru2(CO)5(acetone){μ- (RO)2PN(Et)P(OR)2}2]2+ is readily replaced by various nucleophiles to afford products of the type [Ru2(CO)5L{μ-(RO)2PN(Et)P(OR)2}2]2+, where L is a neutral ligand such as CO, Me2C6H3NC, PhCN, C5H5N, H2O, Me2S or SC4H8, [Ru2Y(CO)5{μ-(RO)2PN(Et)P(OR)2}2]2+, where Y− is an anionic ligand such as Cl−, Br−, I−, CN−, SCN−, MeCO2−, CF3CO2− or [Ru2(μ-Y)(CO)4{μ-(RO)2- PN(Et)P(OR)2}2]+ where Y− is an anionic ligand such as Cl−, Br−, I−, SPh−, S2CNEt2−, MeCO2− or CF3CO2−.  相似文献   

11.
The photochemistry of the tris-substituted clusters Ru3(CO)9(PR3)3 (R=Ph or OMe) with no added ligands, with CO, C2H4, alkynes and H2 is compared and contrasted with results obtained for analogous thermal reactions. Photolysis of a CH2Cl2 solution of Ru3(CO)9(PPh3)3 leads to the metallated complex HRu3(CO)8(PPh3)2(PPh2C6H4). In CCl4, Ru(CO)3(PR3)Cl2 is formed on photolysis of Ru3(CO)9(PR3)3. Photolysis of CO saturated solutions of Ru3(CO)9(PR3)3 leads to Ru(CO)4(PR3). C2H4 saturated solutions of Ru3(CO)9(PR3)3 generate the novel Ru(CO)3(PR3)(2-C2H4) complexes upon photolysis. With C2H2, photolysis of solutions of Ru3(CO)9(PR3)3 leads to the novel complexes Ru(CO)3(PR3)(2-C2H2). Substituted alkyne complexes have been prepared. Thermolysis of Ru3(CO)9(PR3)3 with HCCPh leads to the novel acetylide clusters HRu3(CO)6(PR3)3(3-2-C2Ph). With PhC CPh, only Ru3(CO)9{P(OMe)3}3 reacts, yielding the novel alkyne cluster Ru3(CO)6{P(OMe)3}3(3-2-C2Ph2). With H2, photolysis of CH2Cl2 solutions of Ru3(CO)9(PR3)3 leads to H2Ru(CO)2(PR3)2. Irradiating a 4:1 CH2Cl2 to EtOAc solution of Ru3(CO)9(PR3)3 under an atmosphere of H2 leads to the novel dihydrido species H2Ru3(CO)7(PR3)3. Thermolysis of H2 saturated solutions of Ru3(CO)9(PR3)3 leads to H4Ru4(CO)8(PR3)4.  相似文献   

12.
Syntheses and Crystal Structures of New Sulfido‐bridged Ruthenium Clusters The reaction of S(SiMe3)2 or NaSH with [RuCl2(PPh3)3] or [Ru3Cl8(PEt3)4] leads to the formation of sulfidobridged ruthenium clusters. In this publication the compounds [Ru6S8(PPh3)6][PF6] ( 1 ), [Ru6S8(PPh3)6][RuCl4(PPh3)2] ( 2 ), [Ru6S8(PEt3)6] ( 3 ) and [Ru3S4Cl2(PPh3)3]2 ( 4 ) are described. The structures of these compounds were elucidated by single crystal X‐ray structural analyses.  相似文献   

13.
Reaction of [Ru2(μ-CO)(CO)4{μ-(RO)2PN(Et)(OR)2}2] (R = Me or Pri) with the protonic acids HCl, HBr, HNO3, H2BO2F, CF3COOH, PhSH/HPF6, and H2CO3/HPF6 produces [Ru2A(CO)5 {μ-(RO)2PN(Et)(OR)2}2]+ and/or [Ru2(μ-A)(CO)4{μ-(RO)2PN(Et)(OR)2}2]+ (A = Cl, Br, ON(O)O, OB(F)OH, OC(CF3)O, SPh, and OC(OH)O) via [Ru2H(CO)5{μ-(RO)2PN(Et)(OR)2}2]+ as intermediate; the structure of [Ru2{μ-OB(F)OH}(CO)4{-(PriO)2PN(Et)P(OPri)2}]+ has been established X-ray crystallographically.  相似文献   

14.
The reaction of dibenzoylmethane (HDBM) with [RuCl2(PPh3)3] in benzene in the presence of a supporting base (Et3N) under reflux gives two different complexes, the side product as a green-yellow Ru(III) compound of composition [RuIIICl2(DBM)(PPh3)2] (2) and the main product as a red Ru(II) complex of composition [RuII(DBM)2(PPh3)2] (3). The products were studied by spectroscopic methods, cyclic voltammetry and X-ray single crystal diffraction. The molecular structure of 2 shows a distorted octahedral environment around the Ru atom with two phosphine ligands in trans positions. The octahedral complex 3 shows a cis arrangement of two phosphine ligands.  相似文献   

15.
Treatment of AgNO3 with the Rh-Ru and Cu-Ru hetero bimetallic clusters, [PPN][RhRu5C(CO)14(cod)] and [PPh4]2[CuRu6C(CO)16Cl], afforded novel three-component complexes having one silver-, and two silver-bridges between respective cluster units, [PPN]{Ag[RhRu5C(CO)14(cod)]2} and [PPh4]2{Ag2[CuRu6C(CO)16Cl]2}, respectively. Reaction of the ruthenium-copper cluster [PPh4]2{Cu4[Ru6C(CO)16]2Cl2} (6) with Pd2(dba)3 · CHCl3 gave another three-component cluster [PPh4]2{Cu4Pd2[Ru6C(CO)16]2Cl2} by incorporation of two palladium atoms. However, a similar reaction of 6 with Pt(dba)2 gave only a two-component cluster complex, [PPh4]2{Pt2[Ru6C(CO)15]2}, while the reaction of silver analog [PPN]2{Ag4[Ru6C(CO)16]2Cl2} with Pd2(dba)3 · CHCl3 resulted in the formation of known ruthenium-palladium cluster [PPN]2{Pd4[Ru6C(CO)16]2}. Treatment of 6 with [RhCl(CO)2]2 gave two two-component clusters, [PPh4][RhRu5C(CO)16] and [PPh4]2{Cu7[Ru6C(CO)15]2Cl3}. All the new mixed-metal high nuclearity clusters have been characterized by single crystal X-ray analyses.  相似文献   

16.
In boiling toluene, diphenylacetylene is readily displaced from the dimetallocycle [Ru2(CO)(μ-CO) {μ-C(O)C2Ph2} (η-C5H5)2] by a variety of reagents (P(OMe)3, SO2, R2CN2, Ph2PCH2) to produce [Ru2(CO){P(OMe)3}(μ-CO)2 - (η-C5H5)2] or [Ru2(CO)2(μ-CO)(μ-L)(η-C5H5)2] (L  SO2, CR2, CH2) in high yield.  相似文献   

17.
Corrigendum     
Reactions of NaMn(CO)3 with RuCl2(PMe3)4, RuCl2(dppm)2 and RuCl2(PPh3)3 lead either to an ionic species [Ru2Cl3(PMe3)6]+[Mn(CO)5]? or to metal—metal bonded RuMn compounds such as RuMn(μ-CO)2(CO)3(μ-dppm)2 Cl, and, quite unexpectedly, to the μ-phosphido complex RuMn(μ-PPh2)(CO)6(PPh3)2 via a hydride intermediate.  相似文献   

18.
The clectrochemical behaviour of the complexes [RuII(L)(CO)2Cl2], [RuII(L)(CO)Cl3][Me4N] and [RuII(L)(CO)2(CH3CN)2][CF3SO3]2 (L = 2,2′-bipyridine or 4,4′-isopropoxycarbonyl-2,2′-bipyridine) has been investigated in CH3CN. The oxidation of [Ru(L)(CO)2Cl2] produces new complexes [RuIII(L)(CO)(CH3CN)2Cl]2+ as a consequence of the instability of the electrogenerated transient RuIII species [RuIII(L)(CO)2Cl2]+. In contrast, the oxidation of [RuII(L)(CO)Cl3][Me4N] produces the stable [RuIII(L)(CO)Cl3] complex. In contrast [RuII(L)(CO)2(CH3CN)2][CF3SO3]2 is not oxidized in the range up to the most positive potentials achievable. The reduction of [RuII(L)(CO)2Cl2] and [RuII(L)(CO)2(CH3CN)2][CF3SO3]2 results in the formation of identical dark blue strongly adherent electroactive films. These films exhibit the characteristics of a metal-metal bond dimer structure. No films are obtained on reduction of [RuII(L)(CO)Cl3][Me4N]. The effect of the substitution of the bipyridine ligand by electron-withdrawing carboxy ester groups on the electrochemical behaviour of all these complexes has also been investigated.  相似文献   

19.
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20.
《Polyhedron》1987,6(1):111-117
Treatment of mer,cis-[MnCl(CO)2(dppm-PP′)(dppm-P)] with [Rh2Cl2(CO)4] in the presence of CO and PF6− gives [Cl(OC)2Mn(μ-dppm)2Rh(CO)2]PF6 which might have a bridging chloride ligand. Similar treatment of mer,cis-[MnBr(CO)2(dppm-PP')(dppm-P)] gave [Br(OC)2Mn(μ-dppm)2Rh(CO)2]PF6 which 31P-{1H} NMR spectroscopy showed to be a mixture of two closely related species. Treatment of mer,cis-[MnCl(CO)2(dppm-PP') (dppm-P)] with [Rh2Cl2(CO)4] at −30°C probably gave [Cl(OC)2Mn(μ-dppm)2 Rh(CO)2]Cl but this decomposes above 0°C: the corresponding dibromide was made similarly and is somewhat more stable than the dichloride. Treatment of mer,cis-[MnX(CO)2(dppm-PP')(dppm-P)] (X = Cl or Br) with [IrCl(CO)2(p-toluidine)] and CO-PF6− gave [X(OC)2Mn(μ-dppm)2Ir(CO)2]PF6. Neutral complexes of type [X(OC)2Mn (μ-dppm)2Ir(CO)X'] (X and X' = Cl or Br) are very labile and rapidly decompose to give [Ir(CO)(dppm-PP')2]+ and other (unidentified) products. Treatment of mer,cis-[MnX-(CO)2(dppm-PP')(dppm-P)] with [RhH(CO)(PPh3)3] gave [X(OC)Mn(μ-dppm)2(μ-H)(μ-CO)Rh(CO)] (X = Cl or Br). These heterobimetallic compounds generally showed broad 13P-{1H} resonances for the P nuclei bonded to Mn at ca 20°C due to some coupling with the 55Mn nucleus (I = 100% abundant), but at −30°C these resonances sharpened up due to more rapid quadrupolar relaxation at the lower temperature. NMR and IR data are given.  相似文献   

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