The coordination chemistry of secondary phosphine chalcogenides and their conjugate bases

Walther, B.

doi:10.1016/0010-8545(84)85062-6

Cited by 117 publications

(46 citation statements)

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“…2-phenylethanol (n = 0) or 3phenylpropanol (n = 1), did not exert any effect on the catalytic activity of the complexes. 8 That is why in the present study we focused exclusively on η 6 -3phenylpropanol derivatives given the more convenient and higher-yield access to the corresponding precursor [RuCl2{η 6 :κ 1 (O)-C6H5CH2CH2CH2OH}] (1). 10 Thus, as shown in Scheme 6, a series of [RuCl2(η 6 -C6H5CH2CH2CH2OH){P(OH)R2}] complexes containing symmetrically substituted phosphinous (2a-d) and phosphorous acid (2e-g) ligands could be synthesized by treatment of THF solutions of 1 with the corresponding secondary phosphine oxide or H-phosphonate, respectively, the reactions involving the previously commented P(=O)H to P-OH tautomerization process (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

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Hydrophilic (η⁶-Arene)–Ruthenium(II) Complexes with P–OH Ligands as Catalysts for the Isomerization of Allylbenzenes and C–H Bond Arylation Reactions in Water

2019

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Half-sandwich ruthenium(II) complexes containing η 6-coordinated 3phenylpropanol and phosphinous acid-type ligands, namely [RuCl2(η 6-C6H5CH2CH2CH2OH){P(OH)R2}] (R = Me (2a), Ph (2b), 4-C6H4CF3 (2c), 4-C6H4OMe (2d), OMe (2e), OEt (2f), OPh (2g)), have been synthesized in 44-88% yield by reacting [RuCl2{η 6 :κ 1 (O)-C6H5CH2CH2CH2OH}] (1) with the appropriate pentavalent phosphorous oxide R2P(=O)H. The structure of [RuCl2(η 6-C6H5CH2CH2CH2OH){P(OH)Me2}] (2a) was unequivocally confirmed by X-ray diffraction methods. Compounds 2a-g proved to be catalytically active in the isomerization of allylbenzenes into the corresponding (1-propenyl)benzene derivatives employing water as the sole reaction solvent, with [RuCl2(η 6-C6H5CH2CH2CH2OH){P(OH)(OPh)2}] (2g) showing the best performance and a broad substrate scope (73-93% isolated yields with E/Z ratios around 90:10 employing 1 mol% of 2g, 3 mol% of K2CO3, and performing the catalytic reactions at 80 ºC for 4-24 h). The results herein presented show for the first time the utility of phosphinous acids as auxiliary ligands for metal-catalyzed olefin isomerization processes, reactions in which a cooperative role for the P-OH unit is proposed. On the other hand, the utility of complexes 2a-g as catalysts for ortho-arylation reactions of 2-phenylpyridine in water is also briefly discussed. Scheme 2. Cooperative effect of PR2OH ligands in Ru-catalyzed C-H bond arylation processes. Concerning their preparation, transition metal complexes with phosphinous acids and related P-OH ligands are usually generated by reacting the appropriate metallic precursor with a pentavalent phosphorous oxide (Scheme 3). 1,4,6 In solution, these airstable compounds exist in equilibrium with their trivalent tautomers, which is driven towards the latter by coordination to the metal center. Although much less employed, alternative methods of synthesis involving the hydrolysis of P-C, P-Cl, P-N or P-OR bonds in coordinated phosphines, chlorophosphines, aminophosphines and phosphites, respectively, are also known. 4,7 Scheme 3. Synthesis of metal complexes with phosphinous acid ligands from secondary phosphine oxides. Very recently, we reported that hydrophilic arene-ruthenium(II) complexes containing η 6-coordinated 2-phenylethanol and 3-phenylpropanol ligands [RuCl2{η 6-C6H5CH2(CH2)nCH2OH}(L)] (n = 0, 1; L = phosphine or phosphite; A) are able to catalyze, in combination with NaOH, the transformation of diallyl ether derivatives B into synthetically useful γ,δ-unsaturated aldehydes D in water (Scheme 4). 8 The process

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Section: Resultsmentioning

confidence: 99%

“…Organic solvents were dried by standard methods and distilled under argon before use. 23 All reagents were obtained from commercial suppliers and used without further purification with the exception of the ruthenium complexes [RuCl2{η 6 :…”

Section: Methodsmentioning

confidence: 99%

Hydrophilic (η⁶-Arene)–Ruthenium(II) Complexes with P–OH Ligands as Catalysts for the Isomerization of Allylbenzenes and C–H Bond Arylation Reactions in Water

2019

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“…In general, early transition metals coordinate through the hard oxygen atom, giving M-SPO complexes, and the late transition metals (more employed in homogeneous catalysis) through the soft phosphorus atom, producing M-PA complexes. 11,83,84 Hence, examples of P-coordinated complexes can be found for Fe, Pd, Ir, Au, Pt, Rh and Ru whereas the O-coordination has been described for example with Ti, Cr, Mo, W, Mn, Re and Ru among others. Interestingly, for some cations in the same oxidation state examples of both types of coordination are found in the literature, such as the complexes of Scheme 24 and Scheme 25.…”

Section: Complexation Of Sposmentioning

confidence: 99%

Coordination chemistry and catalysis with secondary phosphine oxides

Gallen

Riéra

Verdaguer

et al. 2019

Catal. Sci. Technol.

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“…27 Excellent review articles describing the diverse coordination chemistry of secondary phosphine oxides 5 have been published. [32][33][34] Accordingly, only selected aspects of the preparation and coordination chemistry of transition-met- (2003)(2004)(2005)(2006)(2007)) from the Deutsche Forschungsgemeinschaft. The development of atom-economical processes using airstable preligands is one of his major research interests.…”

Section: Figurementioning

confidence: 99%

Air- and Moisture-Stable Secondary Phosphine Oxides as Preligands in Catalysis

Ackermann¹

2006

Synthesis

229

108

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The coordination chemistry of secondary phosphine chalcogenides and their conjugate bases

Cited by 117 publications

References 85 publications

Hydrophilic (η⁶-Arene)–Ruthenium(II) Complexes with P–OH Ligands as Catalysts for the Isomerization of Allylbenzenes and C–H Bond Arylation Reactions in Water

Hydrophilic (η⁶-Arene)–Ruthenium(II) Complexes with P–OH Ligands as Catalysts for the Isomerization of Allylbenzenes and C–H Bond Arylation Reactions in Water

Coordination chemistry and catalysis with secondary phosphine oxides

Air- and Moisture-Stable Secondary Phosphine Oxides as Preligands in Catalysis

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The coordination chemistry of secondary phosphine chalcogenides and their conjugate bases

Cited by 117 publications

References 85 publications

Hydrophilic (η6-Arene)–Ruthenium(II) Complexes with P–OH Ligands as Catalysts for the Isomerization of Allylbenzenes and C–H Bond Arylation Reactions in Water

Hydrophilic (η6-Arene)–Ruthenium(II) Complexes with P–OH Ligands as Catalysts for the Isomerization of Allylbenzenes and C–H Bond Arylation Reactions in Water

Coordination chemistry and catalysis with secondary phosphine oxides

Air- and Moisture-Stable Secondary Phosphine Oxides as Preligands in Catalysis

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Hydrophilic (η⁶-Arene)–Ruthenium(II) Complexes with P–OH Ligands as Catalysts for the Isomerization of Allylbenzenes and C–H Bond Arylation Reactions in Water

Hydrophilic (η⁶-Arene)–Ruthenium(II) Complexes with P–OH Ligands as Catalysts for the Isomerization of Allylbenzenes and C–H Bond Arylation Reactions in Water