Dimethylsulfoxide as a Ligand for RhI and IrI Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH3)

Dorta, Reto; Rozenberg, Haim; Shimon, Linda J. W.; Milstein, David

doi:10.1002/chem.200305144

Cited by 49 publications

(57 citation statements)

References 57 publications

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“…Reaction of these two ligands with the cationic complex 56 led to the selective substitution of the two O-bonded ligands, affording [cisIr(dmso-S) 2 (py) 2 ][PF 6 ] and [cis-Ir(dmso-S) 2 (dmbpy)]-[PF 6 ], respectively. 396 Oxidative addition of H 2 to 55 afforded cis,facIrCl(H) 2 (dmso-S) 3 as kinetic product, which evolved to the thermodynamically more stable isomer cis,merIrCl(H) 2 (dmso-S) 3 . 396 396,410 Both dimers were structurally characterized by X-ray crystallography.…”

Section: Iridium−halide−dmso Complexesmentioning

confidence: 99%

“…396 Oxidative addition of H 2 to 55 afforded cis,facIrCl(H) 2 (dmso-S) 3 as kinetic product, which evolved to the thermodynamically more stable isomer cis,merIrCl(H) 2 (dmso-S) 3 . 396 396,410 Both dimers were structurally characterized by X-ray crystallography. Interestingly, in the dicationic species the dmso ligands exhibit both coordination modes: each iridium atom is coordinated to two cis dmso-S molecules and to one dmso-O molecule located trans to the hydride.…”

Section: Iridium−halide−dmso Complexesmentioning

confidence: 99%

“…395,396 Substitution of the dmso ligands in 49 was investigated: treatment of 49 with excess pyridine gave [cis-RhCl(py)(dmso-S) 2 ] by replacement of one dmso, while treatment with 1 equiv of the chelating ligand 4,4′-dimethyl-2,2′-bipyridine (dmbpy) gave [RhCl(dmbpy)(dmso-S)] with concomitant loss of 2 equiv of dmso. 396 The …”

Section: Scheme 50mentioning

confidence: 99%

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Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

2004

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Section: Iridium−halide−dmso Complexesmentioning

confidence: 99%

Section: Iridium−halide−dmso Complexesmentioning

confidence: 99%

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Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

2004

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“…[1][2][3] The oxidation of sulfides is a straightforward and frequently method used to obtain sulfoxides and sulfones. Among various oxidants employed in the reactions, [4][5][6][7][8][9][10][11][12][13][14] hydrogen peroxide is an attractive and environmentally-friendly oxidant owing to its low cost, high availability and cleanliness.…”

Section: Introductionmentioning

confidence: 99%

A peroxotungstate-ionic liquid brush assembly: an efficient and reusable catalyst for selectively oxidizing sulfides with aqueous H2O2 solution in neat water

Ma¹,

Ou²,

Han³

et al. 2012

J. Braz. Chem. Soc.

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Uma sistema catalítico heterogêneo de peroxotungstato realizado em líquido iônico (IL) tipo escova foi sintetizado e aplicado na oxidação seletiva de sulfetos a temperatura ambiente e usando peróxido de hidrogênio 30 wt.% como oxidante terminal e água como solvente. Nenhum cosolvente orgânico ou outro aditivo foi necessário e a reação ocorre com uma quantidade de 1,5-2,0 mol% (baseado no W) de catalisador. Sulfetos alifáticos e aromáticos foram transformados de maneira eficiente e seletiva em seus respectivos sulfóxidos ou sulfonas pelo controle dos equivalentes de peróxido de hidrogênio. Grupos funcionais sensíveis à oxidação, tais como ligações duplas e hidroxila, não foram afetados mesmo com excesso de peróxido de hidrogênio. O catalisador foi recuperado após a reação via filtração e reutilizado pelo menos oito vezes sem perda significativa de atividade.An efficient and reusable heterogeneous catalytic assembly of peroxotungstate held in a ionic liquid (IL) brush was synthesized and an environmentally-friendly procedure was developed for selective oxidation of sulfides at room temperature using 30 wt.% hydrogen peroxide as the terminal oxidant and water as a sole solvent. No organic co-solvent or other additive was needed. A 1.5-2.0 mol% (based on W atom) loading catalyst was found to be sufficient for a smooth and clean reaction. Both aliphatic and aromatic sulfides were efficiently and selectively transformed into their respective sulfoxides or sulfones by simply controlling of equivalents of hydrogen peroxide. In addition to the high catalytic activity, the catalyst exhibits excellent chemoselectivity. Sensitive functional groups, such as double bond and hydroxyl, remained under the oxidation conditions the reaction even with an excess hydrogen peroxide. The catalyst was easily recovered (via simple filtration) and reused at least eight times without a noticeable loss of activity.

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“…No separation of metallic Rh was noticed. While this background reaction has no practical influence on the results of the stereoselective experiments reported hereafter, its presence points out that DMSO has some protecting effect towards the Rh complex, likely due to the formation of some Rh/DMSO species [13]. Addition of 1 equiv.…”

mentioning

confidence: 98%

Expanding the Scope of Atropisomeric Monodentate P‐Donor Ligands in Asymmetric Catalysis: Hydrogen‐Transfer Reduction of α,β‐Unsaturated Acid Derivatives by Rhodium/Ph‐binepine Catalysts

Alberico

Nieddu

Taras

et al. 2006

Helvetica Chimica Acta

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Dedicated to Professor Giambattista Consiglio, a good friend and excellent chemist, for his remarkable contributions to the advancement of stereoselective catalysis A range of a,b-unsaturated acids and esters have been selectively reduced to the corresponding saturated acid derivatives by hydrogen transfer. As the reducing agent, formic acid was used in the presence of Rh I complexes formed with the powerful chiral ligand Ph-binepine (1), an axially chiral binaphthalenetype monodentate P-donor ligand. Very high stereoselectivities (up to 97% ee) were obtained in the case of itaconic acid (2a).Introduction. -The reduction of unsaturated functional groups by means of transition-metal-mediated hydrogen transfer from a suitable hydrogen donor such as i-PrOH or HCOOH has experienced increasing success over the last years [1]. This mild methodology represents a viable alternative to catalytic hydrogenation by molecular H 2 due to its operational simplicity and reduction of the risks associated with the use of an easily inflammable gas of high diffusibility. Significant advances in this area have been achieved in the asymmetric reduction of ketones and imines with catalysts of excellent activity/selectivity based on Ru and Rh complexes with monotosyl-substituted diamines or amino alcohols as chiral modifiers [1a].Less efforts have been devoted to the transfer hydrogenation of C=C bonds. Although this process is thermodynamically favored, even when alcohols are used as H-donors, only the reduction of conjugated C=C bonds is of practical significance, while simple alkenes and dienes are poorly reactive. A perusal of the literature shows that transfer hydrogenation of conjugated acid derivatives such as itaconic acid and a-(acetamido)cinnamic acid selectively takes place at the C=C bond, and stereoselectivities higher than 90% can be sometimes attained in this reaction when performed in the presence of Ru [2] or Rh complexes [3] with chiral bidentate diphosphines such as binap [2], bppm [3a -f], or deguphos [3g]. No example of the application of monodentate phosphines as chiral inducers in this reaction has been reported thus far, in spite of the excellent performances displayed by binaphthalene-templated monoA C H T U N G T R E N N U N G dentate P-ligands [4], such as phosphonites [5], phosphites [6], and phosphoramidites [7], in the Rh-catalyzed hydrogenation of a wide variety of substrates.

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Dimethylsulfoxide as a Ligand for Rh^I and Ir^I Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH₃)

Cited by 49 publications

References 57 publications

Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

A peroxotungstate-ionic liquid brush assembly: an efficient and reusable catalyst for selectively oxidizing sulfides with aqueous H2O2 solution in neat water

Expanding the Scope of Atropisomeric Monodentate P‐Donor Ligands in Asymmetric Catalysis: Hydrogen‐Transfer Reduction of α,β‐Unsaturated Acid Derivatives by Rhodium/Ph‐binepine Catalysts

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