Diruthenium Compound Research Articles

Postmetalation Ligand Modification on the Periphery of a Diruthenium Compound: Toward Novel Metallayne Scaffoldings

A diruthenium compound bearing a peripheral iodo substituent cross-couples with acetylenes under Sonogashira conditions to yield a novel family of diruthenium compounds bearing a peripheral alkyne functionality, which can be further functionalized at the axial positions via a reaction with lithiated butadiynyl.

A unique diruthenium(II, III) unit surrounded by tridentate ligands of N-(2-pyridyl)-2-oxy-5-chlorobenzylaminate

A new metal–metal bonded diruthenium(II, III) compound with a dianionic tridentate ligand, N-(2-pyridyl)-2-oxy-5-chlorobenzylaminate (5-Clsalpy 2−), was synthesized and structurally characterized as Li 2(THF) 4Cl[Ru 2(5-Clsalpy) 3] ( 1). The 5-Clsalpy 2− ligand that acts as a bridging/chelating co-ligand afforded a unique coordination mode of [M–M bridging/equatorial-chelating] in addition to the “common” mode of [M–M bridging/axial-chelating] around the diruthenium unit of 1.

Homo- and heterobimetallic complexes of ruthenium(II) and osmium(II) with pyrazole-3,5-dicarboxylic acid and 2,2′-bipyridine as co-ligands. Synthesis, structure, stereochemistry, spectroscopy and redox activities

Mononuclear, homodinuclear and heterodinuclear ruthenium(II) and osmium(II) complexes of composition [(bpy)2Ru(H2pzdc)](ClO4)·3H2O (1), [(bpy)2Os(H2pzdc)](ClO4)·3H2O (2), [(bpy)2Ru(pzdc)Ru(bpy)2](ClO4)·H2O (3), [(bpy)2Os(pzdc)Os(bpy)2](ClO4)·H2O (4) and [(bpy)2Ru(pzdc)Os(bpy)2](ClO4)·H2O (5) have been synthesized with pyrazole-3,5-dicarboxylic acid (H3pzdc) and 2,2′-bipyridine (bpy). Complexes 3–5 isolated solely in the homochiral forms have been characterized by their 1H and {1H1H} COSY NMR spectra. The crystal structures determined for 3 and 5 have revealed that the two compounds are isostructural and the diruthenium compound 3 is present in the rac(ΛΛ/ΔΔ) form, while the osmiumruthenium compound 5 is present as the enantiomeric pair (ΛΛ and ΔΔ). The metal-centered oxidation and bipyridine-centred reduction in 1–5 take place reversibly. As compared with the diruthenium complex 3, the stepwise oxidation of the metal centers in the diosmium complex 4 take place at less positive potentials by 0.45 V. The equilibrium constants for the comproportionation reaction MIIMII+MIIIMIII⇌2MIIMIII are found to be almost equal (ca. 6×102) for the diruthenium and diosmium species. From pH-dependent redox potential measurements the acid dissociation constants for the mononuclear complexes 1 and 2 have been determined. The luminescence spectral behavior of the complexes have been investigated in methanol–ethanol (1:4) solution (at 300 K) and in glassy state (77 K) and the quantum yields for the ruthenium(II) complexes are reported.

Tetrakis(N,N'-dimethylbenzamidinato)diruthenium(III) compounds bearing axial chloro and alkynyl ligands: a new family of redox rich diruthenium compounds.

Novel diruthenium(III) compound Ru(2)(DMBA)(4)Cl(2) (1, DMBA = N,N'-dimethylbenzamidinate) was obtained via refluxing Ru(2)(OAc)(4)Cl with dimethylbenzamidine in the presence of LiCl and Et(3)N under ambient atmosphere. Metathesis reactions between 1 and MC(2)Y (M = Li and Na) yielded bis-alkynyl derivatives Ru(2)(DMBA)(4)(C(2)Y)(2) (Y = SiMe(3) (2a), H (2b), Ph (2c), and C(2)SiMe(3) (3a)), and further desilylation of 3a using K(2)CO(3) resulted in Ru(2)(DMBA)(4)(C(4)H)(2) (3b). Compound 1 is paramagnetic (S = 1), while compounds 2 and 3 are diamagnetic. The single-crystal X-ray diffraction study revealed that the Ru-Ru distances are 2.3224(7), 2.4501(6), and 2.4559(6) A for 1, 2a, and 3b, respectively. A strong Ru-C sigma-bond in alkynyl adducts was implied by the short Ru-C distances in 2a (1.955(4) A) and 3b (1.952[5] A). All the compounds undergo three one-electron redox processes, an oxidation and two reductions, and the reversibility of redox couples depends on the nature of axial ligands.

A new metal–metal bonded diruthenium(II,III) compound bridged by the dianionic tridentate ligand N-(2-pyridyl)-2-oxy-5-chlorobenzylaminate (5-Clsalpy2−)

The ligand-substitution reaction of Ru2(O2CCH3)4Cl with the tridentate ligand N-(2-pyridyl)-2-oxy-5-chlorobenzylaminate dianion (5-Clsalpy2−) led to the unique diruthenium(II,III) compound [{Na(THF)2}{Ru2(O2CCH3)2(5-Clsalpy)2}]·THF (1·THF) which revealed the characteristic 1-D chain structure of the repeating unit [–Na–O–Ru–Ru–O–]∞ and rich redox chemistry.

Reactions of acetonitrile di-iron μ-aminocarbyne complexes; synthesis and structure of [Fe 2(μ-CNMe 2)(μ-H)(CO) 2(Cp) 2

The complexes [Fe 2{μ-CN(Me)R}(μ-CO)(NCMe)(CO)(Cp) 2]SO 3CF 3 (R=Me, 2a; 2,6-Me 2C 6H 3, 2b; CH 2Ph, 2c), easily obtained from the corresponding [Fe 2{μ-CN(Me)R}(μ-CO)(CO) 2(Cp) 2]SO 3CF 3 ( 1a– c) precursors, react with NBu 4CN affording the cyano complexes [Fe 2{μ-CN(Me)R}(μ-CO)(CN)(CO)(Cp) 2] ( 3a– c) by displacement of the MeCN ligand. The analogous reaction with NBu 4Cl leads to the formation of [Fe 2{μ-CN(Me)R}(μ-CO)(Cl)(CO)(Cp) 2] ( 4a– b). The μ-hydride complexes [Fe 2{μ-CN(Me)R}(μ-H)(CO) 2(Cp) 2] ( 5a– b) have been prepared by reaction of 1a– b with NaBH 4. The corresponding diruthenium compound [Ru 2(μ-CNMe 2)(μ-H)(CO) 2(Cp) 2] ( 6) has been similarly obtained from [Ru 2(μ-CNMe 2)(μ-CO)(NCMe)(CO)(Cp) 2]SO 3CF 3. The X-ray molecular structure of 5a is that expected for cis isomers of this family of compounds. It shows a chiral conformation of the C 5H 5 ligands and the crystals are a conglomerate of enantiomeric individuals. NMR spectra of the various compounds, which are indicative of the presence of α–β or cis– trans isomeric mixtures, are reported and discussed.

Synthesis of tetracarboxylatediruthenium(II) compounds: reduction and disproportionation reactions of diruthenium(II,III) units. Crystal structure of Ru 2(μ-O 2CCOPh) 4(thf) 2

The treatment of Ru 2Cl(μ-O 2CR) 4 with zinc amalgam in thf, under a nitrogen atmosphere, leads to the isolation of diruthenium(II) compounds of the type Ru 2(μ-O 2CR) 4 (R = Me ( 1), Ph ( 2), C 6H 4- o-Cl ( 3), C 6H 4- p-CMe 3 ( 4), CHMe 2 ( 5), CMe 3 ( 6), CHEt 2 ( 7)). These unsolvated diruthenium complexes are soluble in coordinating solvents giving bis(adducts) of the type Ru 2(μ-O 2CR) 4(S) 2 (S = solvent molecule: MeOH, thf). The substitution of the axial solvent molecules by OPPh 3 affords new compounds of the type Ru 2(μ-O 2CR) 4(OPPh 3) 2 (R = Me ( 8), Ph ( 9), C 6H 4- o-Cl ( 10), C 6H 4- p-CMe 3 ( 11), CHMe 2 ( 12), CMe 3 ( 13), CHEt 2 ( 14)). From the reaction of Ru 2Cl)μ-O 2CMe) 4 with phenylglyoxylic acid the diruthenium(II) compound Ru 2(μ-O 2CCOPh) 4(thf) 2 ( 15) has been isolated in the absence of any additional reducing agent. The crystal structure of 15 has been determined by X-ray crystallography. The structure of this complex shows a diruthenium(II) unit bridged by four phenylglyoxylate ligands with the axial positions occupied by thf molecules, the RuRu distance being 2.2736(8) Å.

Bis-ethanedithiolate triruthenium cluster complexes from the reaction of Ru3(CO)12 with 1,2,5, 6-tetrathiacyclooctane

The reaction of 1,2,5,6-tetrathiacyclooctane with Ru3(CO)12 in methylene chloride solvent at 40°C has yielded two new isomericbis-thane-1,2-dithiolate triruthenium carbonyl cluster complexes:anti-Ru3(CO)7(μ-SCH2CH2S)2, 1 andsyn-Ru3(CO)7(μ-SCH2CH2S)2,2, and the previously reported diruthenium compound, Ru2(CO)6(μ-SCH2CH2S).3 in 24 %, 5 %, and 26 % yields, respectively. Compounds1 and2 were characterized by a single crystal X-ray diflraction analyses. Both compounds consist of a open triangular triruthenium clusters with seven terminal carbonyl ligands and a bridging ethanedithiolate ligand across each of the metal metal bonds in the complex. When heated to 60° C, compound1 was trans[formed into a mixture of2 and3. Crystallographic data for1: Ru3S4O7C11H8, space group, P21/a,a= ll.830(2)A,b= 10.576(1)A,c= 16.012(1)A,β= 100.53(2)°,Z=4, 1808 reflections,R= 0.029. For2: Ru3 S4O7C11H8, space group P1,a= 9.945(l)A,b= 11.323(1)A.c= 9,788(1)A,a= 108.73(1)°,β= 104,67(1)°,y= 103.59(2)°,Z = 2, 2046 rellections.R = 0.021.

Synthesis and X-ray Structure of the First Nonpolymeric Chlorotetrakis(carboxylato)- diruthenium(II,III) Compound

Synthesis and X-ray Structure of the First Nonpolymeric Chlorotetrakis(carboxylato)- diruthenium(II,III) Compound

A Novel Binuclear Ruthenium(III) Compound Triply Bridged by Chloride and Disulfide Ligands, [RuCl{P(OMe)3}2(μ-Cl)2(μ-S2)RuCl{P(OMe)3}2

Abstract A diruthenium compound with a novel Ru2(S2)Cl2 core has been synthesized. The X-ray crystal study shows that the disulfide ligand bridges the ruthenium atoms in a cis manner with the S-S distance of 1.971(4) Å. The compound has a redox potential of −0.57 V (vs. Ag+/Ag) and a characteristic absorption band at 737 nm.

Reactivity of triphenylphosphine toward RuIIRuIIICl(O2CAr)4: syntheses, molecular structures, and spectroscopic and electrochemical properties of RuIIRuIII(OH2)Cl(MeCN)(O2CAr)4(PPh3)2 and RuII2(OH2)(MeCN)2(O2CAr)4(PPh3)2

By the reaction of Ru2Cl(O2CAr)4 (1) and PPh3 in MeCN-H2O the diruthenium(II,III) and diruthenium(II) compounds of the type Ru2(OH2)Cl(MeCN)(O2CAr)4(PPh3)2 (2) and Ru2(OH2)(MeCN)2(O2CAr)4(PPh3)2 (3) were prepared and characterized by analytical, spectral, and electrochemical data (Ar is an aryl group, C6H4-p-X; X = H, OMe, Me, Cl, NO2). The molecular structure of Ru2(OH2)Cl(MeCN)(O2CC6H4-p-OMe)4(PPh3)2 was determined by X-ray crystallography. Crystal data are as follows: triclinic, P1BAR, a = 13.538 (5) angstrom, b = 15.650 (4) angstrom, c = 18.287 (7) angstrom, alpha = 101.39 (3)-degrees, beta = 105.99 (4)-degrees, gamma = 97.94 (3)-degrees, V = 3574 angstrom 3, Z = 2. The molecule is asymmetric, and the two ruthenium centers are clearly distinguishable. The Ru(III)-Ru(II), Ru(III)-(mu-OH2), and Ru(II)-(mu-OH2) distances and the Ru-(mu-OH2)-Ru angle in [{Ru(III)Cl(eta-1-O2CC6H4-p-OMe)(PPh3)}(mu-OH2)(mu-O2CC6H4-p-OMe)2{Ru(II)(MeCN)(eta-1-O2CC6H4-p-OMe)(PPh3)}] are 3.604 (1), 2.127 (8), and 2.141 (10) angstrom and 115.2 (5)-degrees, respectively. The compounds are paramagnetic and exhibit axial EPR spectra in the polycrystalline form. An intervalence transfer (IT) transition is observed in the range 900-960 nm in chloroform in these class II type trapped mixed-valence species 2. Compound 2 displays metal-centered one-electron reduction and oxidation processes near -0.4 and +0.6 V (vs SCE), respectively in CH2Cl2-TBAP. Compound 2 is unstable in solution phase and disproportionates to (mu-aquo)diruthenium(II) and (mu-oxo)diruthenium(III) complexes. The mechanistic aspects of the core conversion are discussed. The molecular structure of a diruthenium(II) compound, Ru2(OH2)(MeCN)2(O2CC6H4-p-NO2)4(PPh3)2.1.5CH2Cl2, was obtained by X-ray crystallography. The compound crystallizes in the space group P2(1)/c with a = 23.472 (6) angstrom, b = 14.303 (3) angstrom, c = 23.256 (7) angstrom, beta = 101.69 (2)-degrees, V = 7645 angstrom 3, and Z = 4. The Ru(II)-Ru(II) and two Ru(II)-(mu-OH2) distances and the Ru(II)-(mu-OH2)-Ru(II) angle in [{(PPh3)-(MeCN)(eta-1-O2CC6H4-p-NO2)Ru}2(mu-OH2)(mu-O2CC6H4-p-NO2)2] are 3.712 (1), 2.173 (9), and 2.162 (9) angstrom and 117.8 (4)-degrees, respectively. In both diruthenium(II,III) and diruthenium(II) compounds, each metal center has three facial ligands of varying pi-acidity and the aquo bridges are strongly hydrogen bonded with the eta-1-carboxylato facial ligands. The diruthenium(II) compounds are diamagnetic and exhibit characteristic H-1 NMR spectra in CDCl3. These compounds display two metal-centered one-electron oxidations near +0.3 and +1.0 V (vs SCE) in CH2Cl2-TBAP. The overall reaction between 1 and PPh3 in MeCN-H2O through the intermediacy of 2 is of the disproportionation type. The significant role of facial as well as bridging ligands in stabilizing the core structures is observed from electrochemical studies.

Dibenzo[b,i]-1,4,8,11-tetraazacyclotetradecine complexes. 3. Preparation and molecular structure of an unprecedented diruthenium(II) compound, Ru2(Htmtaa)(O2CCH3)3(PhCCPh)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDibenzo[b,i]-1,4,8,11-tetraazacyclotetradecine complexes. 3. Preparation and molecular structure of an unprecedented diruthenium(II) compound, Ru2(Htmtaa)(O2CCH3)3(PhCCPh)F. A. Cotton and Joanna CzuchajowskaCite this: J. Am. Chem. Soc. 1991, 113, 9, 3427–3431Publication Date (Print):April 1, 1991Publication History Published online1 May 2002Published inissue 1 April 1991https://doi.org/10.1021/ja00009a030RIGHTS & PERMISSIONSArticle Views145Altmetric-Citations17LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (635 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

The first structurally characterized diruthenium(II,III) complex with four bridging arylcarboxylato ligands

The diruthenium(II,III) compound [Ru 2Cl(O 2CC 6H 4- p-OMe) 4](H 2O) 0.25 ( 1) has been prepared and its crystal structure determined by X-ray studies. The crystals belong to the triclinic space group, P 1 , and the asymmetric unit consists of one full dimer and two half dimers. The {Ru 2(O 2CC 6H 4- p-OMe) 4 +} units are bridged by chloride ions into an infinite zigzag chain, with an average RuCl distance and RuClRu angle of 2.567(2) Å and 121.0(1)°, respectively. The average RuRu distance of 2.286(1) Å in 1 is comparable with that in analogous tetra-alkylcarboxylates, Ru 2Cl(O 2CR) 4 and tetra-amidates, Ru 2Cl(ArCONH) 4.

Reaction of tetraacetatochlorodiruthenium(II,III) with pyridine-2-carboxylic acid. X-Ray crystal structures of tris(pyridine-2-carboxylato-κN,O)ruthenium(III) monohydrate and trans-bis(pyridine-2-carboxylato-κN,O)bis(triphenylphosphine)ruthenium(II)–methanol(1/2)

The reaction of [Ru2Cl(µ-O2CMe)4] with pyridine-2-carboxylic acid (Hpyca) in methanol-water (1:1) affords a ruthenium(III) complex, [Ru(pyca)3]·H2O 1, and a diruthenium(II) compound, [Ru2(pyca)4]2. The reaction of both complexes with PPh3 leads to the new compound [Ru(pyca)2(PPh3)2]·2MeOH 3. The crystal structures of 1 and 3 have been determined. Crystals of both are monoclinic: 1, space group C2/c, a= 30.415(7), b= 8.506(1), c= 13.943(3)A, β= 94.55(2)°, Z= 8; 3, space group P21/n, a= 9.578(1), b= 20.540(3), c= 11.501(2)A, β= 98.57(1)°, Z= 2. Compound 1 consists of Ru(pyca)3 units linked by water molecules; the ruthenium environment is pseudo-octahedral with the ligands giving a mer arrangement. Compound 3 shows a trans disposition for the phosphine ligands with the pyridine-2-carboxylate ligands in the equatorial plane. In these complexes the pyridine-2-carboxylate ligands are co-ordinated in a bidentate mode through a carboxylate O atom and the pyridine nitrogen.

Synthesis and reactions of directly bonded zirconiumruthenium heterobimetallic complexes

The directly bonded zirconiumruthenium heterobimetallic compounds Cp 2(X)ZrRu(CO) 2Cp ( X = Cl, OCMe 3, CH 3, CH 2CH 3) were synthesized by reaction of Cp 2(X)ZrCl with K + Cp(CO) 2Ru −. The zirconiumdiruthenium compound Cp 2Zr[Ru(CO) 2Cp] 2 ( 21) was synthesized by reaction of Cp 2ZrI 2 with K +Cp(CO) 2Ru −. Reaction of 21 with a variety of ligands led to expulsion of Cp(CO) 2RuH and formation of C 5H 4-Zr products or intermediates. Reaction of 21 with CO produced Cp 2(CO)Zr(μ-η 1,η 5- C 5H 4)Ru(CO) 2 ( 22), with PMe 3 produced Cp 2Zr(μ-CO)(μ-η 1,η 5-C 5H 4)Ru(CO)(PMe 3) ( 23), and with CH 2CH 2 produced Cp 2Zr(μ-CH 2CH 2C 5H 4)Ru(CO) 2 ( 26). All three of these reactions proceeded at the same rate which was independent of incoming ligand concentration. All three reactions are proposed to involve rate determining formation of the reactive intermediate Cp 2Zr(μ-η 1,η 5-C 5H 4)Ru(CO) 2 ( I). The reaction of CO adduct 22 and H 2 led to hydrogenolysis of the ZrC 5H 4 bond and to the formation of Cp 2Zr(μ-CO)(μ-OCH)Ru(CO)Cp ( 32). Labelling studies demonstrated that reversible formation of both zirconium formyl and ruthenium formyl intermediates occurs during the reduction of 22 to 32.

Preparation and molecular and electronic structures of a diamagnetic diruthenium(II) compound, Ru2[(p-CH3C6H4)NNN(p-CH3C6H4)

Preparation and molecular and electronic structures of a diamagnetic diruthenium(II) compound, Ru2[(p-CH3C6H4)NNN(p-CH3C6H4)

ChemInform Abstract: Reactivity of PPh3 Towards Ru2Cl(O2CR)4 (R: Me, Ph) in Alcoholic Medium: A Novel Decarbonylation Process Mediated by a Diruthenium Compound.

AbstractThe title reaction in refluxing methanol, ethanol, and butanol is studied by IR and 1H NMR spectroscopy.

Reactivity of PPh 3 towards Ru 2Cl(O 2CR) 4 (R = Me, Ph) in alcoholic medium: a novel decarbonylation process mediated by a diruthenium compound

On montre que les alcools contenant 2 atomes H s'oxydent en aldehyde correspondant en presence d'un intermediaire actif qui serait une espece di-Ru contenant PPh 3 dans sa sphere de coordination. Formation quantitative de Ru 2 O(PPh 3 ) 2 (O 2 CR) 4

ChemInform Abstract: A New Mixed‐Ligand Diruthenium(II) Compound. Synthesis and Characterization of [Ru2Cl(Me2PCH2PMe2)2(PhNpy)2][BPh4

AbstractThe title compound (II) was prepared by reaction of (I), which was obtained from an in situ reaction of Ru2Cl(O ‐ Ac)4 with Z‐anilinopyridine, and bis(dimethylphosphino)methane in the presence of chlorotrimethylsilane in toluene and isolated as the BPh4 salt.

A new mixed-ligand diruthenium(II) compound. Synthesis and characterization of [Ru2Cl(Me2PCH2PMe2)2(PhNpy)2][PBh4

The title compound was prepared by reacting Ru/sub 2/Cl(O/sub 2/CCH/sub 3/)/sub 2/(PhNpy)/sub 2/(PhNHpy) and (dimethylphosphino)methane (dmpm) in the presence of chlorotrimethylsilane in toluene. The compound was isolated as a crystalline mass by cooling a methanolic solution of the complex in the presence of Na(BPh/sub 4/). The crystals of composition (Ru/sub 2/Cl(dmpm)/sub 2/(PhNpy)/sub 2/)(BPh/sub 4/).1.5MeOH belong to the monoclinic system, space group P2/sub 1//n, with the following unit cell dimensions: a = 14.064 (5) A, b = 24.047 (8) A, c = 18.642 (4) A, ..cap alpha.. = ..gamma.. = 90/sup 0/, ..beta.. = 110.52 (2)/sup 0/, V = 5905 (3) A/sup 3/, Z = 4. The cationic species (Ru/sub 2/Cl(dmpm)/sub 2/(PhNpy)/sub 2/)/sup +/ consists of a diruthenium(II) core held by two dmpm and two PhNpy/sup -/ ligands. The orientation of the PhNpy/sup -/ ligands is unidirectional. The ruthenium that is bonded to pyridine nitrogens has an axial Cl/sup -/ ligand while the axial site on the other ruthenium is vacant because of two pendant phenyl rings on the amine nitrogen atoms. The Ru-Ru distance is 2.340 (2) A. The Ru-Cl, average Ru-P, and average Ru-N distances are 2.480 (5) A, 2.396 (5) A, and 2.122 (12) A, respectively. The averagemore » torsion angle in N-Ru-Ru-N and P-Ru-Ru-P is 19.84/sup 0/. The compound is moderately stable in air in the solid state and is soluble in common organic solvents. The complex is paramagnetic and has a magnetic moment of 2.6 ..mu../sub B/ (at 308K), corresponding to two unpaired spins. The metal-metal bond order is 2.0 according to the sigma/sup 2/..pi../sup 4/delta/sup 2/)(delta*..pi..*)/sup 4/ ground-state electronic configuration. 29 references, 4 figures, 3 tables.« less