Arene-ruthenium(<scp>ii</scp>) complexes with hydrophilic P-donor ligands: versatile catalysts in aqueous media

Crochet, Pascale; Cadierno, Victorio

doi:10.1039/c4dt01494d

Cited by 57 publications

(25 citation statements)

References 124 publications

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“…11a,31 Also in this case an outstanding yield of 94% was obtained for the catalytic reaction with 3a (Table 1, entry 8), which is far better than the 57% that resulted with the PyPPh 2 ligand (entry 9). 11a This performance is in line with that with DME as solvent (entries 1 and 4) by also showing that the catalytic reaction with ligand 3a outperforms that with Ph 2 PPy.…”

Section: Resultsmentioning

confidence: 72%

Iminophosphanes: Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles

et al. 2017

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Highly stable iminophosphanes, obtained from alkylating nitriles and reaction of the resulting nitrilium ions with secondary phosphanes, were explored as tunable P-monodentate and 1,3-P,N bidentate ligands in rhodium complexes. X-ray crystal structures are reported for both κ1 and κ2 complexes with the counterion in one of them being an unusual anionic coordination polymer of silver triflate. The iminophosphane-based ruthenium(II)-catalyzed hydration of benzonitrile in 1,2-dimethoxyethane (180 °C, 3 h) and water (100 °C, 24 h) and under solvent free conditions (180 °C, 3 h) results in all cases in the selective formation of benzamide with yields of up to 96%, thereby outperforming by far the reactions in which the common 2-pyridyldiphenylphosphane is used as the 1,3-P,N ligand.

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Section: Resultsmentioning

confidence: 72%

Iminophosphanes: Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles

et al. 2017

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“…[1,3,4] An attractive alternative methodi st he homogenous [1][2][3][4]6] or heterogeneous [7][8][9][10][11] metal-catalyzed nitrile hydration. [1,[12][13][14][15][16][17] Ru II and Ru IV complexes with nitrogen-containing phosphine ligands (for example, [RuCl 2 (h 6 -arene)(P(NMe 2 ) 3 )]) have shown significant activity for nitrile hydration. [2] Ruthenium complexesh ave been utilized as efficient and versatile catalysts for nitrile hydration to amides.…”

Section: Introductionmentioning

confidence: 99%

“…With water as a reagent, and many of the product amides having modest water solubility,n itrile hydration is well suited towardsa queous-phase catalysis. [9,[13][14][15][16][17][18][19][20][21][22] Our group has been interested in the development of water-soluble phosphine ligandsf or use in catalysis. [1,[12][13][14][15][16][17] Ru II and Ru IV complexes with nitrogen-containing phosphine ligands (for example, [RuCl 2 (h 6 -arene)(P(NMe 2 ) 3 )]) have shown significant activity for nitrile hydration.…”

Section: Introductionmentioning

confidence: 99%

“…[1,[12][13][14][15][16][17] Ru II and Ru IV complexes with nitrogen-containing phosphine ligands (for example, [RuCl 2 (h 6 -arene)(P(NMe 2 ) 3 )]) have shown significant activity for nitrile hydration. [9,[13][14][15][16][17][18][19][20][21][22] Our group has been interested in the development of water-soluble phosphine ligandsf or use in catalysis. Our work has largely focused on ruthenium complexes containing the air-stable and water-soluble 1,3,5-triaza-7-phosphaadamantane (PTA) [23][24][25] and derivatives for possible aqueous-phase catalysis.…”

Section: Introductionmentioning

confidence: 99%

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Aqueous‐Phase Nitrile Hydration Catalyzed by an In Situ Generated Air‐Stable Ruthenium Catalyst

Ounkham

Weeden

Frost

2019

Chemistry A European J

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RuCl 2 (PTA) 4 (PTA = 1,3,5-triaza-7-phosphaadamantane) is an active, recyclable, air-stable,a queous-phase nitrile hydration catalyst. The development of an in situ generated aqueous-phase nitrileh ydration catalyst (RuCl 3 ·3 H 2 O + 6equivalents PTA) is reported.T he activity of the in situ catalyst is comparable to RuCl 2 (PTA) 4 .T he effects of [PTA] on the activity of the reaction were investigated:t he catalytic activity, in general, increases as the pH goes up, which shows ap ositive correlation with [PTA].T he pH effectsw ere furthere xplored for both the in situ and RuCl 2 (PTA) 4 cata-lyzed reactioni np hosphate buffer solutionsw ith particular attention given to pH 6.8 buffer.I ncreased catalytic activity was observed at pH 6.8 versus waterf or both systems with turnover frequency (TOF) up to 135 h À1 observed for RuCl 2 (PTA) 4 and 64 h À1 for the in situ catalyst. Catalystl oading down to 0.001 mol %w as examinedw ith turnover numbers as high as 22 000 reported. Similar to the preformed catalyst, RuCl 2 (PTA) 4 ,t he in situ catalyst could be recycled more than five times withouts ignificant loss of activity from eitherw ater or pH 6.8 buffer. Results and DiscussionThe relatively simple synthesis [34,35] and high activity of RuCl 2 (PTA) 4 as ac atalystf or the hydration of nitrilesp rompted us to investigate utilizingRuCl 3 and PTAasaninsitu generated [a] Dr.

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“…[1][2][3] Ruthenium compounds have been utilized as catalysts for nitrile hydration with [(η 6 -arene)RuCl 2 PR 3 ] complexes as some of the most efficient and versatile catalysts with good substrate tolerance. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] Ruthenium complexes of 1,3,5-triaza-7-phosphaadamtane (PTA) [11,12,[15][16][17] and derivatives [10] have exhibited high activity and selectivity for the hydration of nitriles to amides. We have shown that some ruthenium complexes with PTA or PTA derivatives are active for nitrile hydration in the presence of air, removing the need to run these reactions under inert atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Water soluble diphosphine ligands based on 1,3,5-triaza-7-phosphaadamantane (PTA-PR2): Synthesis, coordination chemistry, and ruthenium catalyzed nitrile hydration

Sears

Lee

Frost

2015

Inorganica Chimica Acta

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Please cite this article as: J.M. Sears, W-C. Lee, B.J. Frost, Water Soluble Diphosphine ligands based on 1,3,5-triaza-7-phosphaadamantane (PTA-PR 2 ): synthesis, coordination chemistry, and ruthenium catalyzed nitrile hydration, Inorganica Chimica Acta (2015), doi: http://dx.ABSTRACT: Two chiral chelating 1,3,5-triaza-7-phosphaadamantane (PTA) derivatives were synthesized, in racemic form, by addition of ClP i Pr 2 or ClP(N i Pr) 2 (CH 2 ) 2 to lithiated PTA. PTA-P i Pr 2 (1) and PTA-P(N i Pr) 2 (CH 2 ) 2 (2) were isolated in good yield, 73 % and 56 % respectively, and fully characterized by multinuclear NMR spectroscopy, mass spectrometry, and X-ray crystallography. PTA-P i Pr 2 is highly air sensitive, but stable and somewhat soluble in degassed water. PTA-P(N i Pr) 2 (CH 2 ) 2 (2) is air-stable, but decomposes in water over the course of hours. Two tungsten tetracarbonyl complexes were prepared by addition of the PTA-PR 2 to [W(CO) 4 (pip) 2 ] and characterized by NMR and IR spectroscopies and X-ray crystallography in the case of [W(CO) 4 (PTA-P i Pr 2 )]. Based on IR spectroscopy PTA-P i Pr 2 (1) is more electron donating than PTA-P(N i Pr) 2 (CH 2 ) 2 (2) or the previously published PTAPPh 2 . Products isolated from the reaction of [(η 6 -toluene)RuCl 2 ] 2 with two equivalents of 1 were found to contain monodentate (κ 1 ), bidentate (κ 2 ), and possibly bridging coordination modes of PTA-P i Pr 2 . These ruthenium complexes were explored as catalysts for aqueous phase nitrile hydration. Of the ruthenium explored [(η 6 -toluene)RuCl 2 (κ 1 -PTA-P i Pr 2 )] (7) was the most active towards nitrile hydration. In the presence of air at 100 °C 7 converted various nitriles to the respective amides with 43-99% conversions in 7 h.

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Arene-ruthenium(ii) complexes with hydrophilic P-donor ligands: versatile catalysts in aqueous media

Cited by 57 publications

References 124 publications

Iminophosphanes: Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles

Iminophosphanes: Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles

Aqueous‐Phase Nitrile Hydration Catalyzed by an In Situ Generated Air‐Stable Ruthenium Catalyst

Water soluble diphosphine ligands based on 1,3,5-triaza-7-phosphaadamantane (PTA-PR2): Synthesis, coordination chemistry, and ruthenium catalyzed nitrile hydration

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