Monomerisation of [Rh2(1,3-Bis-(Diphenylphosphino)-Propane)2(μ2-Cl)2] Detected by Pulsed Gradient Spin Echo Spectroscopy and 31P Nmr Monitoring of Metathesis Experiments

Mannu, Alberto; Ferro, Mónica; Möller, Saskia; Heller, Detlef

doi:10.3184/174751918x15333065984578

Cited by 12 publications

(11 citation statements)

References 29 publications

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“…= solvent), already detected for several solvents and diphosphines[79]. Such species can exist in equilibrium with many other intermediates, including dinuclear [Rh2(diphosphine)2(2-Cl)2][79], trinuclear [Rh3(DPPP)3(μ3-OMe)2] +[80], and mononuclear [Rh(PP)X][81,82]. Recently, Baráth[83] suggested a catalytic cycle for the TH reaction mediated by dinuclear [Rh2(DPPP)2(2-Cl)2] (Scheme 10).…”

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confidence: 93%

Transfer Hydrogenation from 2-propanol to Acetophenone Catalyzed by [RuCl2(η6-arene)P] (P = monophosphine) and [Rh(PP)2]X (PP = diphosphine, X = Cl−, BF4−) Complexes

2020

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The reduction of ketones through homogeneous transfer hydrogenation catalyzed by transition metals is one of the most important routes for obtaining alcohols from carbonyl compounds. The interest of this method increases when opportune catalytic precursors are able to perform the transformation in an asymmetric fashion, generating enantiomerically enriched chiral alcohols. This reaction has been extensively studied in terms of catalysts and variety of substrates. A large amount of information about the possible mechanisms is available nowadays, which has been of high importance for the development of systems with excellent outcomes in terms of conversion, enantioselectivity and Turn Over Frequency. On the other side, many mechanistic aspects are still unclear, especially for those catalytic precursors which have shown only moderate performances in transfer hydeogenation. This is the case of neutral [RuCl 2 (η 6 -arene)(P)] and cationic [Rh(PP) 2 ]X (X = anion; P and PP = monoand bidentate phosphine, respectively) complexes. Herein, a summary of the known information about the Transfer Hydrogenation catalyzed by these complexes is provided with a continuous focus on the more relevant mechanistic features. Abstract:The reduction of ketones through homogeneous transfer hydrogenation catalyzed by transition metals is one of the most important routes for obtaining alcohols from carbonyl compounds. The interest of this method increases when opportune catalytic precursors are able to perform the transformation in an asymmetric fashion, generating enantiomerically enriched chiral alcohols. This reaction has been extensively studied in terms of catalysts and variety of substrates. A large amount of information about the possible mechanisms is available nowadays, which has been of high importance for the development of systems with excellent outcomes in terms of conversion, enantioselectivity and Turn Over Frequency. On the other side, many mechanistic aspects are still unclear, especially for those catalytic precursors which have shown only moderate performances in transfer hydeogenation. This is the case of neutral [RuCl2( 6 -arene)(P)] and cationic [Rh(PP)2]X (X = anion; P and PP = mono-and bidentate phosphine, respectively) complexes. Herein, a summary of the known information about the Transfer Hydrogenation catalyzed by these complexes is provided with a continuous focus on the more relevant mechanistic features.The possibility to reduce ketones to alcohols in an enantioselective way through ATH represents a milestone in the asymmetric catalysis, as chiral alcohols are employed as intermediates, as well as end-products in many industries, including fragrancies and pharmaceutics [2]. In addition, the protocol can be extended to a general C=X polar substrate (X = O, N), allowing the synthesis of chiral alcohols [2], amines, and many corresponding derivatives [3].Recent applications of such protocol have allowed the valorization of biomass by extracting lignin [4], or for the production of biofuels [5].Historically, a ...

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confidence: 93%

Transfer Hydrogenation from 2-propanol to Acetophenone Catalyzed by [RuCl2(η6-arene)P] (P = monophosphine) and [Rh(PP)2]X (PP = diphosphine, X = Cl−, BF4−) Complexes

2020

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“…The presented results significantly extend the initially proposed reaction pathway [10a] (Figure S25) and allow for the refinement of the mechanistic picture (Figure 11). After an experimentally confirmed monomerization of 7 to 11 of the precatalyst 7, [19] coordination of 1-octyne occurs, as described earlier. [10a] However, the results also indicate that the alkyne complex 14 is not asymmetric, as previously assumed but has a symmetrical structure and is neutral in nature due to the coordination of two alkyne molecules.…”

Section: Figurementioning

confidence: 77%

Catalyst Deactivation During Rhodium Complex‐Catalyzed Propargylic C−H Activation

Möller

Jannsen

Rüger

et al. 2021

Chemistry A European J

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“…The 13 P{ 1 H}NMR spectra of prepared complexes (3,4) showed singlet at δ27.83ppm, 30.02ppm respectively this clearly indicated that the two phosphorus atoms were equivalent and the dppp and dppb ligands behaved as bidentate ligands. 28,29…”

Section: Infrared Spectramentioning

confidence: 99%

Synthesis, Characterization and Antibacterial Activity of some Hg(II) Complexes with Mixed Benzyl 2-(2-oxoindolin-3-ylidene) Hydrazinecarbodithioate and Phosphines or Amines Ligands

2021

TJNPR

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activity. 15,16 The anticancer evaluation of a substantial number of metal complexes containing isatin-based ligands has been described as antitumor compounds, especially Mg(II), Co(II), Ni(II), and Cu(II) complexes, with different coordination geometries and reactivities. 17 Materials and MethodsAll the chemicals, reagents and solvents for the synthesis of compounds were supplied and used without more purification. The melting point of the prepared complexes was recorded on Automatic (SMP30) melting point apparatus. The molar conductivity of 10 -3 M freshly DMSO solution of prepared complexes was measured using (Starter 3100c) digital conductivity meter at 25 o C. Microanalyses for carbon, hydrogen, nitrogen and sulfur were carried out using an Elementar vario El III CHN elemental analyzer. The IR spectra of the prepared complexes as KBr pellets were recorded using a Shimadzu FT-IR 8400S spectrophotometer (400-4000 cm -1 ). NMR spectra were acquired on a Bruker 400 MHz spectrometer in DMSO-d6 as a solvent. The isolates of the pathological bacteria that were used in the research obtained from the laboratories of the Department of Life Sciences in the College of Education for Pure Sciences at the University of Tikrit. Preparation of benzyl 2-(2-oxoindolin-3-ylidene)hydrazinecarbodithioate (BHT) ligandThe benzyl 2-(2-oxoindolin-3-ylidene)hydrazinecarbodithioate (BHT) Prepared by two steps: First step: Preparation of S-Benzyldithiocarbazate (SBDTC). This compound was synthesized as previously reported, 18 the melting point was 124 o C where it was at 124-125 o C in the literature. 19 Second step: To the hot solution of S-benzyldithiocarbazate, SBDTC (1.36g, 0.01 mol) in ethanol (35 mL), an equimolar amount of isatin

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Monomerisation of [Rh₂(1,3-Bis-(Diphenylphosphino)-Propane)₂(μ₂-Cl)₂] Detected by Pulsed Gradient Spin Echo Spectroscopy and ³¹P Nmr Monitoring of Metathesis Experiments

Cited by 12 publications

References 29 publications

Transfer Hydrogenation from 2-propanol to Acetophenone Catalyzed by [RuCl2(η6-arene)P] (P = monophosphine) and [Rh(PP)2]X (PP = diphosphine, X = Cl−, BF4−) Complexes

Transfer Hydrogenation from 2-propanol to Acetophenone Catalyzed by [RuCl2(η6-arene)P] (P = monophosphine) and [Rh(PP)2]X (PP = diphosphine, X = Cl−, BF4−) Complexes

Catalyst Deactivation During Rhodium Complex‐Catalyzed Propargylic C−H Activation

Synthesis, Characterization and Antibacterial Activity of some Hg(II) Complexes with Mixed Benzyl 2-(2-oxoindolin-3-ylidene) Hydrazinecarbodithioate and Phosphines or Amines Ligands

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