The tris(triphenylphosphine)osmium zerovalent complexes Os(CO)2(PPh3)3, .Os(CO)(CNR)(PPh3)3, Os(CO)(CS)(PPh3)3, Os(CS)(cNR)(PPh3)3 and derived compounds

Detailed procedures for the syntheses of Os(CO)₂(PPh₃)₃, Os(CO)(CNR)-(PPh₃)₃ (R = p-tolyl), Os(CO)(CS)(PPh₃)₃ and Os(CS)(CNR)(PPh₃)₃, together with the derived complexes Os(CO)₂(CS)(PPh₃)₂, Os(CO)(CS)(CNR)(PPh₃)₂, Os(η²-C₂H₄)(CO)(CNR)(PPh₃)₂, Os(η²-C₂H₄)(CO)(CS)(PPh₃)₂, Os(η²CS₂)(CO)₂-(PPh₃)₂, Os(η²CS₂)(CO)(CS)(PPh₃)₂, Os(η²-CS₂)(CO)(CNR)(PPh₃)₂, Os(η²PhC₂Ph)(CO)₂(PPh₃)₂ and OsH(C2Ph)(CO)₂(PPh₃)₂ are described.     

Synthesis of [TpRu(CO)(PPh3)]2(μ-CHCHCHCHC6H4CHCHCHCH) from Wittig reactions

Treatment of [Ru(CHCHCH₂PPh₃)X(CO)(PPh₃)₂]⁺ (X=Cl, Br) with KTp (Tp=hydridotris(pyrazolyl)borate) and NaBPh₄ produced [TpRu(CHCHCH₂PPh₃)(CO)(PPh₃)]BPh₄. Reaction of RuHCl(CO)(PPh₃)₃ with HCCCH(OEt)₂ produced Ru(CHCHCH(OEt)₂)Cl(CO)(PPh₃)₂, which reacted with KTp to give TpRu(CHCHCHO)(CO)(PPh₃). Treatment of [TpRu(CHCHCH₂PPh₃)(CO)(PPh₃)]BPh₄ with NaN(SiMe₃)₂ and benzaldehyde produced TpRu(CHCHCHCHPh)(CO)(PPh₃). The later complex was also produced when TpRu(CHCHCHO)(CO)(PPh₃) was treated with PhCH₂PPh₃Cl/NaN(SiMe₃)₂. The bimetallic complex [TpRu(CO)(PPh₃)]₂(μ-CHCHCHCHC₆H₄CHCHCHCH) was obtained from the reaction of [TpRu(CHCHCH₂PPh₃)(CO)(PPh₃)]BPh₄ with NaN(SiMe₃)₂ and terephthaldicarboxaldehyde.     

Carbonylation of alkenyl-complexes of ruthenium. The formation of complexes containing,alkene or acyl ligands,and the reaction of the acyl complexes with methanol

The unsaturated complexes RuCl(CO)(RC=CHR′)(PPh₃)₂ react with CO to give the dicarbonyl complexes RuCl(CO)₂(RC=CHR′)(PPh₃)₂ or the η²-acyl complexes RuCl(CO)(O=CC(R)=CHR′)(PPh₃)₂, depending on the R and R′ groups. The RuCl(CO)(O=CC(Me)=CHMe)(PPh₃)₂ complex reacts with methanol to give RuCl(CO)(O₂CC(Me)=CHMe)(PPh₃)₂, which structure has been established by an X-ray diffraction study.     

Synthesis and Application of Ruthenium(II) Alkenyl Complexes with Perylene Fluorophores for the Detection of Toxic Vapours and Gases

A series of new ruthenium(II) vinyl complexes has been prepared incorporating perylenemonoimide (PMI) units. This fluorogenic moiety was functionalised with terminal alkyne or pyridyl groups, allowing attachment to the metal either as a vinyl ligand or through the pyridyl nitrogen. The inherent low solubility of the perylene compounds was improved through the design of poly-PEGylated (PEG=polyethylene glycol) units bearing a terminal alkyne or a pyridyl group. By absorbing the compounds on silica, vapours and gases could be detected in the solid state. The reaction of the complexes [Ru(CH=CH-Per^Im)Cl(CO)(py-3PEG)(PPh₃)₂] and [Ru(CH=CH-3PEG)Cl(CO)(py-Per^Im)(PPh₃)₂] with carbon monoxide, isonitrile or cyanide was found to result in modulation of the fluorescence behaviour. The complexes were observed to display solvatochromic effects and the interaction of the complexes with a wide range of other species was also studied. The study suggests that such complexes have potential for the detection of gases or vapours that are toxic to humans.     

Chemistry of a family of semiquinone monochelates of carbonyl ruthenium(II) generated by reacting quinones with hydridic species

The reactions of [Ru(H)(Cl)(CO)(PPh₃)₃] with 3,5-di-tert-butyl-o-benzoquinone (dbq) and 3,4,5,6-tetrachloro-o-benzoquinone (tcq) have afforded the corresponding semiquinone complexes [Ru^II(dbsq)(Cl)(CO)(PPh₃)₂] and [Ru^II(tcsq)(Cl)(CO)(PPh₃)₂], respectively. The reaction of [Ru(H)₂(CO)(PPh₃)₃] with tcq has furnished [Ru^II(tcsq)(H)(CO)(PPh₃)₂]. Structure determination of [Ru(dbsq)(Cl)(CO)(PPh₃)₂] has revealed that it is a model semiquinonoid chelate with two equal C---O lengths ( 1.291(6) and 1.296(6) Å). The complexes are one-electron paramagnetic (1.85μ_B) and their EPR spectra in fluid media display a triplet structure (g2.00) due to superhyperfine coupling with two trans-³¹P atoms (A_iso17 G). The stretching frequency of the CO ligand increases by 20 cm⁻¹ in going from [Ru(dbsq)(Cl)(CO)(PPh₃)₂] to [Ru(tcsq)(Cl)(CO)(PPh₃)₂] consistent with electron withdrawal by chloro substituents. For the same reason the E_1/2 values of the cyclic voltammetric quinone/semiquinone and semiquinone/catechol couples undergo a shift of 500 mV to higher potentials between [Ru(dbsq)(Cl)(CO)(PPh₃)₂] and [Ru(tcsq)(Cl)(CO)(PPh₃)₂].     

Erratum

The hydrido-thiocarbonyl osmium(II) complexes OsH₂(CS)(PPh₃)₃, OsHCl(CS)(PPh₃)₃, OsH(OClO₃)(CS)(PPh₃)₃, OsHCl(CS)(CNR)(PPh₃)₂ and [OsH(CS)(CO)(PPh₃)₃]⁺, (R = p-tolyl), have been derived from OsCl₂(CS)(PPh₃)₃ and [OsH(CS)(CO)(PPh₃)₃]⁺, the latter can be deprotonated to give the zerolavent complex, Os(CS)(CO)(PPh₃)₃.     

Extrusion of halogens from aromatic compounds by transition metal complexes. Reaction of IrCl(CO)(PPh3)2 with halogenated benzaldehydes

Summary The chlorobenzaldehydes, 2-bromo-4-tolualdehyde and 2-iodobenzaldehyde react with IrCl(CO)(PPh₃)₂ at 190 to 220° to give PhIrCl₂(CO)(PPh₃)₂,p-tolyl IrBr₂(CO)(PPh₃)₂ and PhIrCl₂(CO)(PPh₃), respectively. Iodo-and bromobenzene form PhIrCl(Hal)(CO)(PPh₃)₂ complexes, whereas chlorobenzene does not react under these conditions. Halogen transfer from the aromatic to the metal atom in the reaction of halobenzaldehydes, and halogen extrusion in various homogeneously catalyzed processes, are assumed to follow similar reaction patterns.     

Hydrosilylation of n- and o-heterocyclic aldehydes in the presence of RhI,RuII, and PdII complexes

The hydrosilylation of 2-formylpyridine, 2-formyl-6-methylpyridine, 2-formylfuran, and 2-formyl-5-methylfuran with triethylsilane in the presence of Rh(PPh₃)₃Cl, Rh(PPh₃)₃(CO)H, Rh(PPh₃)₂(C0)Cl, Ru(PPh₃)₃Cl₂, Ru(PPh₃)₂(CO)₂Cl₂, and Pd(PPh₃)₂Cl₂ was studied. Silyl ethers of the corresponding hetarylcarbinols were obtained in high yields. The formation of products of dehydrocondensation of the silyl ethers is observed in the hydrosilylation of methyl-substituted aldehydes; this process does not occur in the presence of ruthenium complexes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1372–1380, October, 1988.     

Synthesis of low-valent thiocarbonyl complexes via 1,2-elimination of methylthiol from cis-metal-hydrido-dithiomethylester complexes. Os(cs)(CO)2(PPh3)2 and IrCl(CS)(PPh3)2.

[OS(η²-CS₂Me)(CO)₂(PPH₃)₂]⁺ and [Ir(η²-CS₂Me)Cl(CO)(PPh₃)₂)⁺ react with NaBH₄ giving OsH(CS₂Me)(CO)₂(PPh₃)₂ and IrH(CS₂Me)Cl(CO)(PPh₃)₂ respectively; These compounds contain mutually $\text{cis}$ hydride and η¹-dithiomethylester ligands and upon heating undergo 1,2-elimination of MeSH producing Os(CS)(CO)₂(PPh₃)₂ and IrCl(CS)(PPh₃)₂.     

Coordination,oligomerisation and transfer hydrogenation of acetylenes by some ruthenium and osmium carboxylates: Crystal and molecular structures of bis(trifluoroacetato)carbonyl-(methanol) bis(triphenylphosphine)ruthenium(II) and (1,4-diphenylbut-1-en-3-yn-2-yl)trifluoroacetato-(carbonyl) bis(triphenylphosphine)ruthenium(II)

The hydrides [MH(O₂CCF₃)(CO)(PPh₃)₂] (M = Ru or Os) react with disubstituted acetylenes PhCCPh and PhCCMe to afford vinylic products [M{C(Ph)CHPh}(O₂CCF₃)(CO)(PPh₃)₂] and [M{C(Ph)CHMe}(O₂CCF₃)(CO) (PPh₃)₂]/[M{C(Me)CHPh}(O₂CCF₃)(CO)(PPh₃)₂] respectively. Acidolysis of these products with trifluoroacetic acid in cold ethanol liberates cis-stilbene and cis-PhHCCHMe respectively thus establishing the cis-stereochemistry of the vinylic ligands. The complexes [M(O₂CCF₃)₂(CO)(PPh₃)₂] formed during the acidolysis step undergo facile alcoholysis followed by β-elimination of aldehyde to regenerate the parent hydrides [MH(O₂CCF₃)(CO)(PPh₃)₂] and thereby complete a catalytic cycle for the transfer hydrogenation of acetylenes. The molecular structure of the methanol-adduct intermediate, [Ru(O₂CCF₃)₂(MeOH)(CO)(PPh₃)₂] has been determined by X-ray methods and shows that the coordinated methanol is involved in H-bonding with the monodentate trifluoroacetate ligand [MEO-H---OC(O)CF₃; O...O = 2.54 Å]. The hydrides [MH(O₂CCF₃)(CO) (PPh₃)₂]react with 1,4-diphenylbutadiyne to afford the complexes [M{C(CCPh)CHPh} (O₂CCF₃)(CO)(PPh₃)₂]. The ruthenium product, which has also been obtained by treatment of [RuH(O₂CCF₃)(CO)(PPh₃)₂] with phenylacetylene, has been shown by X-ray diffraction methods to contain a 1,4-diphenylbut-1-en-3-yn-2-yl ligand. The osmium complexes [Os(O₂CCF₃)₂(CO)(PPh₃)₂], [OsH(O₂CCF₃)(CO)(PPh₃)₂] and [Os{C(CCPh)CHPh}(O₂CCF₃)(CO)(PPh₃)₂] all serve as catalysts for the oligomerisation of phenylacetylene. Acetylene reacts with [Ru(O₂CCF₃)₂(CO)(PPh₃)₂] in ethanol to afford the vinyl complex [Ru(CHCH₂)(O₂CCF₃)(CO)(PPh₃)₂].     

Synthesis of organometallic hydrotris(pyrazol-1-yl)boratoruthenium(II) complexes

The reactions of K[HB(pz)₃] (pz = pyrazol-1-yl) with the coordinatively unsaturated σ-vinyl complexes [Ru(CRCHR)Cl(CO)(PPh₃)₂] (R = H, Me, C₆H₅) proceed with loss of a chloride and a phosphine ligand to provide the compounds [Ru(CRCHR)(CO)(PPh₃){HB(pz)₃}] in high yield. Similar treatment of the complex [Ru(C₆H₄Me-4)Cl(CO)(PPh₃)₂] leads to the related σ-aryl derivative [Ru(C₆H₄Me-4)(CO)(PPh₃){HB(pz)₃}] whilst the complex [RuClH(CO)(PPh₃)₃] treated successively with diphenylbutadiyne and K[HB(pz)₃] provides the unusual derivative [Ru{C(CCPh)CHPh}(CO)(PPh₃){HB(pz)₃}].     

Reaction of alkenyl carbonyl ruthenium(II) complexes with t-butyl isocyanide. Synthesis of η1-acylruthenium(II) complexes by intramolecular CO insertion

Reaction of Ru(CO)Cl(CHCHR)(PPh₃)₂ or Ru(CO)Cl(CHCHR)(PPh₃)₂L (L = py, Me₂Hpz) with 1 equivalent of t-butyl isocyanide gives the alkenyl derivatives Ru(CO)Cl(CHCHR)(PPh₃)₂(t-BuNC). When an excess of isocyanide is used, further reaction results in intramolecular CO insertion to yield η¹-acyl complexes [Ru(COCHCHR) (t-BuNC)₃(PPh₃)₂]Cl. Related complexes were obtained from [Ru(CO)(CHCHR)(MeCN)₂(PPh₃)₂]PF₆ and an excess of isocyanide.     

The interaction of an osmium-carbon triple bond with copper(I), silver(I) and gold(I) to give mixed dimetallocyclopropene species and the structures of Os(AgCl) (CR) Cl(CO) (PPh3)2

The osmium carbyne complex, Os(CR)Cl(CO)(PPh₃)₂, (R  p-tolyl) reacts with Group I halides to form the mixed dimetallocyclopropene species, $\text{Os(Cul)(C}$R)Cl(CO)(PPh₃)₂, $\text{Os(AgCl)(C}$R)Cl(CO)(PPh₃)₂, $\text{Os(AuCl)(C}$R)Cl(CO)(PPh₃)₂, and [$\text{Os[Ag(OClO}{}_3\text{)](C}$R)Cl(CO)(MeCN)(PPh₃)₂] ClO₄ X-ray crystal structure determination of $\text{Os(AgCl)(C}$R)Cl(CO)(PPh₃)₂ confirms the presence of a three-membered ring and the structure can be viewed as the “acetylene-like” interaction of an osmium—carbon triple bond with AgCl. In acid solution AgCl is precipitated and an alkylidene complex results from proton addition to the carbyne ligand.     

Synthesis and reactions of isocyanate and carbamoyl complexes of rhenium

Re(CO)₂(NO)(PPh₃)₂ reacts with aroyl azides RCON₃ (R = C₆H₅, p-CH₃C₆H₄) in benzene to form isocyanate complexes of formula Re(CO)(NO)-(PPh₃)₂(RCONCO) (I). When the reaction is carried out in protic solvents such as ethanol, carbamoyl derivatives of formula Re(NCO)(NO)(PPh₃)₂-(CONHCOR) (II) are obtained, which give Re(NCO)(NO)(PPh₃)₂(CO)(NHCOR) when dissolved in chloroform, a terminal carbonyl ligand being formed from the carbamoyl group.I can be transformed into II by reaction with gaseous HCl, via [Re(CO)-(NO)(PPh₃)₂ {C(OH)=NCOR}]⁺Cl^- followed by anion exchange with NaN₃. II reacts with mineral acids HX (X = Cl, BF₄) to give amide derivatives of formula [Re(NCO)(NO)(PPh₃)₂(CO)(NH₂COR)]⁺ X^- which when X = Cl can be easily transformed into Re(NCO)(NO)(PPh₃)₂(CO)Cl, the amide ligand being removed. Both the protonation reactions of I and II are reversible. IR and ¹H NMR data of the new compounds and the mechanisms of formation of I and II are reported and discussed.     

Reactions of osmium coordinated formaldehyde. Synthesis of complexes of selenoformaldehyde and telluroformaldehyde

Os(η²-CH₂O)(CO)₂(PPh₃)₂ reacts with CSe₂ to form a metallacycle O$\text{s(CH}{}_2\text{OC[Se}$]Se)(CO)₂(PPh₃)₂. This compound breaks down to Os(η²-CH₂Se)(CO)₂(PPh₃)₂ with probable loss of COSe. An alternative route to Os(η²-CH₂Se)(CO)₂(PPh₃)₂ and also Os(η²-CH₂Te)(CO)₂(PPh₃)₂ is through reaction of Os(CH₂I)I(CO)₂(PPh₃)₂ with SeH^? and TeH^?, respectively. HCl with Os(η²-CH₂E)(CO)₂(PPh₃)₂ (E = Se or Te) gives OsCl(EMe)(CO)₂(PPh₃)₂ while methyl iodide gives [Os(η²-CH₂EMe)(CO)₂ - (PPh₃)₂] I. BH₄^? reacts with these cations to cleave the CE bond and form Os(CH₃)(EMe)(CO)₂(PPh₃)₂.     

ortho-metallation reactions involving some triphenyl phosphite complexes of osmium

Osmium triphenylphosphine complexes, OsH₄(PPh₃)₃, OsH₂ (CO)(PPh₃)₃ and OsHCl(CO)(PPh₃)₃ react with triphenyl phosphite in boiling organic solvents to yield triphenyl phosphite derivatives which subsequently undergo ortho-metallation reactions.     

Synthesis, crystal, molecular, and electronic structures of hydride carbonyl ruthenium(II) complexes with pseudohalide ligands

Two pseudohalide hydride carbonyl ruthenium(II) complexes with formulae: [RuH(N₃)(CO)(PPh₃)₃] (1) and [RuH(NCO)(CO)(PPh₃)₃] (2) have been synthesized by the reactions of [RuHCl(CO)(PPh₃)₃] with sodium azide or sodium cyanate, respectively, and are compared with the previously described thiocyanate analog [RuH(NCS)(CO)(PPh₃)₃]. The molecular structures of the new compounds were determined by X-ray crystallography and their spectroscopic properties have been studied. Based on the crystal structures, computational investigations have been carried out in order to determine the electronic structures of the complexes. The electronic spectra were calculated with the use of time-dependent DFT methods, and the electronic spectra of the transitions were correlated with the molecular orbitals of the complexes.     

Metallkomplexe mit biologisch wichtigen Liganden. LXXXII. Triphenylphosphan-Molybdän-, Wolfram-, Ruthenium- und Iridium-Komplexe mit N-acylierten α-Aminocarboxylaten

Metal Complexes of Biological Important Ligands. LXXXII. Triphenylphosphine Molybdenum, Tungsten, Ruthenium, and Iridium Complexes of N-Acyl-α-Aminocarboxylates The reactions of the hydrido complexes RuHCl(CO) · (PPh₃)₃, RuH₂(PPh₃)₄ and IrH₃(PPh₃)₃ with N-acyl-α-aminocarboxylates give the carboxylate complexes RuCl(O₂CCHRNHCOR′)(CO)(PPh₃)₂ ( 1–3 ), RuH(O₂CCHRNHCOR′)(PPh₃)₃ ( 4–6 ) and IrH₂(O₂CCH₂NHCOPh)(PPh₃)₃ ( 7 ). The structure of RuCl · (O₂CCHNHCOPh)(CO)(PPh₃)₂ ( 1 ) has been determined by x-ray diffraction. The triphenylphosphine complexes MBr · (O₂CCH₂NHCOR)(CO)₂(PPh₃)₂ (M = Mo, W) ( 8–12 ) and Mo(O₂CCHRNHCOR′)₂(CO)₂(PPh₃)₂ ( 13–17 ) are formed from MBr₂(CO)₂(PPh₃)₂ (M = Mo, W) with one or two equivalents of N-acyl-a-aminoacidates, respectively.     

Chemistry of vinylidene complexes

The reactions of Cp(CO)₂Re=C=CHPh (2) with M(PPh₃)₄ (M = Pd, Pt) gave the μ-vinylidene complexes Cp(CO)₂RePd(μ-C=CHPh)(PPh₃)₂ (3) and Cp(CO)₂RePt(μ-C=CHPh)(PPh₃)₂ (1), respectively. The substitution of Ph₂PCH₂PPh₂ (dppm) for the PPh₃ ligands in 1 resulted in the formation of Cp(CO)RePt(μ-C(1)=C(2)HPh)(μ-CO)(dppm) (4). The structure of complex 4 has been determined by single-crystal X-ray diffraction analysis. The structural and spectroscopic characteristics of complexes 1, 3, and 4 were compared with the corresponding parameters of the manganese-containing analogs Cp(CO)₂MnPd(μ-C=CHPh)(PPh₃)₂ (5), Cp(CO)₂MnPt(μ-C=CHPh)(PPh₃)₂ (6) and Cp(CO)₂MnPt(μ-C=CHPh)(dppm) (7).     

Diyne coordination chemistry: Reactions of [RuClH(CO)(PPh3)3] with diphenylbutadiyne and bis(phenylethynyl)mercury

The reaction of the hydridometal complex [RuClH(CO)(PPh₃)₃] with 1,4-diphenyl-butadi-1,3-yne has been investigated and found to proceed with monoinsertion to give a coordinatively unsaturated σ-vinyl complex [Ru-{C(CCPh)CHPh} Cl(CO)(PPh₃)₂], which is also the major product of the reaction of [RuClH(CO) (PPh₃)₃] with [Hg(CCPh)₂].