Insertion reactions of the 16-electron complexes MHCl(CO)[P(CHMe2)3]2 (M = Ru, Os) with alkynes. The x-ray crystal structure of [(E)-PhCH:CHOs(Cl)(CO)[P(CHMe2)3]2

Werner, Helmut; Esteruelas, Miguel A.; Otto, H.

doi:10.1021/om00142a019

Cited by 181 publications

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“…We note that in the case of the vinyl osmium complex [OsCl(CH=CHPh)(CO)(PiPr 3 ) 2 ], the E-configuration of the OsCH=CHPh fragment was confirmed by an X-ray diffraction analysis. [15] Treatment of 2 with NaOAc in THF led to the displacement of chloride by acetate. The proposed structure of 6 (see Scheme 1) is mainly supported by the IR spectrum, which shows two C-O stretching modes at 1520 and 1470 cm -1 , that are diagnostic for a bidentate OAc ligand.…”

Section: Resultsmentioning

confidence: 99%

Hydrido‐Osmium(II), ‐Osmium(IV) and‐Osmium(VI) Complexes with Functionalized Phosphanes as Ligands

Richter

Werner

2009

Eur J Inorg Chem

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Reaction of five‐coordinate [OsHCl(CO)(PiPr3)2] (1) with the chelating phosphane iPr2PCH2CO2Me gave six‐coordinate [OsHCl(CO)(PiPr3){κ2(P,O)‐iPr2PCH2C(=O)OMe}] (2), which upon treatment with CO and O2 afforded the 1:1 adducts [OsHCl(CO)(L)(PiPr3){κ(P)‐iPr2PCH2CO2Me}] (3, 4) by partial opening of the chelate ring. The vinyl complex [OsCl(CH=CHPh)(CO)(PiPr3){κ2(P,O)‐iPr2PCH2C(=O)OMe}] (5) was obtained from 2 and PhC≡CH by insertion of the alkyne into the Os–H bond. Reaction of 2 with sodium acetate led to metathesis of the anionic ligands and formation of [OsH(η2‐O2CCH3)(CO)(PiPr3){κ(P)‐iPr2PCH2CO2Me}] (6). Osmium(VI) compounds [OsH6(PiPr2R)2] with R = CH2CH2OMe (12), CH2CO2Me (13) and CH2CO2Et (14), and [OsH6(PiPr3){κ(P)‐iPr2PCH2CH2NMe2}] (16) were prepared from osmium(IV) precursors and shown to rapidly react with O2 and primary alcohols. Exploratory studies revealed that the catalytic activity of the hexahydrido complexes in the hydrogen transfer reaction from 2‐propanol to cyclohexanone and acetophenone depends on the type of the functionalized phosphane and is best for R = CH2CH2OMe. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Resultsmentioning

confidence: 99%

Hydrido‐Osmium(II), ‐Osmium(IV) and‐Osmium(VI) Complexes with Functionalized Phosphanes as Ligands

Richter

Werner

2009

Eur J Inorg Chem

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“…This is largely due to well-established synthetic routes such as hydrometallation and the reaction of coordinated alkynes with electrophiles or nucleophiles (Scheme 1). [1] Since the discovery of hydrometallation of alkynes by the compounds [RuHCl(CO)L 2/3 ] (L = PiPr 3 , [2] PPh 3 [3] ), the resulting alkenyl complexes have been the subject of much pioneering work by the groups of Werner, [10] Esteruelas [11] Santos, [12] and Caulton and Eisenstein [13] covering functional-group transformation, ligand exchange and theoretical calculations. The hydride complexes themselves are known for their ability to catalyse hydrogenation, [14,15] hydrocarbonylation [16] and hydrosilylation [15,17] reactions as well as the formation of diynes.…”

Section: Introductionmentioning

confidence: 99%

“…Common routes to alkenyl complexes: (A) RCϵCR; [2,3] (B) Nu -, nucleophile is β to metal; [4] (C) E + , electrophile is β to metal; [5] (D) Nu -, nucleophile is α to metal; [6] (E) rearrangement yields alkenyl; [7] (F) H 2 C=C(X)R, X = halide; [8] (G) loss of H + to produce α-alkoxyalkenyls. [9] groups exploring the effect of polydentate donors on the structure and reactivity of alkenyl complexes.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic, Structural and Theoretical Investigation of Alkenyl Ruthenium Complexes Supported by Sulfur–Nitrogen Mixed‐Donor Ligands

et al. 2006

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“…The catalyst Ru(CH CHPh)Cl(CO)(PCy 3 ) 2 was prepared according to the literature method. [13] Hydrogenation Operation Procedures A given quantity of SBR was dissolved in an appropriate amount of cyclohexane. The catalysts were weighed and placed in a catalyst addition device in the reactor.…”

Section: Methodsmentioning

confidence: 99%

Hydrogenation of Styrene‐Butadiene Rubber Catalyzed by Ru(CHCHPh)Cl(CO)(PCy₃)₂

Pan

Rempel

2004

Macromol. Rapid Commun.

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Summary: The hydrogenation of a copolymer of styrene and butadiene (SBR) catalyzed by Ru(CHCHPh)Cl(CO)(PCy3)2 was experimentally investigated within the temperature range of 120–160 °C, at P of 300–1 200 psi, and a catalyst concentration of 10–78 × 10−6 M. Special attention was paid to minimizing the catalyst metal residue and crosslinking in the product. The results indicated that high‐quality hydrogenated SBR was achieved without crosslinking and the metal residue was less than 7 ppm without a post‐treatment.IR spectra of the styrene–butadiene rubber before (a) and after (b) hydrogenation with the Ru(CHCHPh)Cl(CO)(PCy3)2 catalyst were observed as reported here. The disappearance of all characteristic absorbencies of CC (724, 910, 967, and 994 cm−1) suggests nearly quantitative hydrogenation of the CC bonds.imageIR spectra of the styrene–butadiene rubber before (a) and after (b) hydrogenation with the Ru(CHCHPh)Cl(CO)(PCy3)2 catalyst were observed as reported here. The disappearance of all characteristic absorbencies of CC (724, 910, 967, and 994 cm−1) suggests nearly quantitative hydrogenation of the CC bonds.

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Insertion reactions of the 16-electron complexes MHCl(CO)[P(CHMe2)3]2 (M = Ru, Os) with alkynes. The x-ray crystal structure of [(E)-PhCH:CHOs(Cl)(CO)[P(CHMe2)3]2

Cited by 181 publications

References 0 publications

Hydrido‐Osmium(II), ‐Osmium(IV) and‐Osmium(VI) Complexes with Functionalized Phosphanes as Ligands

Hydrido‐Osmium(II), ‐Osmium(IV) and‐Osmium(VI) Complexes with Functionalized Phosphanes as Ligands

Spectroscopic, Structural and Theoretical Investigation of Alkenyl Ruthenium Complexes Supported by Sulfur–Nitrogen Mixed‐Donor Ligands

Hydrogenation of Styrene‐Butadiene Rubber Catalyzed by Ru(CHCHPh)Cl(CO)(PCy₃)₂

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Insertion reactions of the 16-electron complexes MHCl(CO)[P(CHMe2)3]2 (M = Ru, Os) with alkynes. The x-ray crystal structure of [(E)-PhCH:CHOs(Cl)(CO)[P(CHMe2)3]2

Cited by 181 publications

References 0 publications

Hydrido‐Osmium(II), ‐Osmium(IV) and‐Osmium(VI) Complexes with Functionalized Phosphanes as Ligands

Hydrido‐Osmium(II), ‐Osmium(IV) and‐Osmium(VI) Complexes with Functionalized Phosphanes as Ligands

Spectroscopic, Structural and Theoretical Investigation of Alkenyl Ruthenium Complexes Supported by Sulfur–Nitrogen Mixed‐Donor Ligands

Hydrogenation of Styrene‐Butadiene Rubber Catalyzed by Ru(CHCHPh)Cl(CO)(PCy3)2

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Hydrogenation of Styrene‐Butadiene Rubber Catalyzed by Ru(CHCHPh)Cl(CO)(PCy₃)₂