Formation of [Pt(η3-allyl)(TPPTS)2]+ from Reaction of cis-Pt(Cl)2(TPPTS)2 with Alkenols in Water

Helfer, Derrik S.; Phaho, David S.; Atwood, Jim D.

doi:10.1021/om050540a

Cited by 11 publications

(16 citation statements)

References 51 publications

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“…4-Hydroxybutan-2-one (2w): 36 colorless oil; 1 H NMR (500 MHz, CDCl 3 ) δ 3.84 (q, J = 4.9 Hz, 2H), 2.79 (br s, 1H), 2.73−2.67 (m, 2H), 2.21−2.18 (m, 3H); 13 C{ 1 H} NMR (125 MHz, CDCl 3 ) δ 209. 5, 57.6, 45.3, 30.4. 2-Oxopropyl acetate (2x): 37 pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 4.66 (s, 2H), 2.17 (s, 3H), 2.16 (s, 3H); 13 C{ 1 H} NMR (125 MHz, CDCl 3 ) δ 201.5, 170.1, 68.2, 25.9, 20.3.…”

Section: ■ Conclusionmentioning

confidence: 99%

Regioselective Hydration of Terminal Alkynes Catalyzed by a Neutral Gold(I) Complex [(IPr)AuCl] and One-Pot Synthesis of Optically Active Secondary Alcohols from Terminal Alkynes by the Combination of [(IPr)AuCl] and Cp*RhCl[(R,R)-TsDPEN]

Wang

Liu

et al. 2015

J. Org. Chem.

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A neutral gold(I) complex [(IPr)AuCl] (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene) was found to be a highly effective catalyst for the hydration of terminal alkynes, including aromatic alkynes and aliphatic alkynes. The desired methyl ketones were obtained in high yields with complete regioselectivities. Furthermore, a series of optically active secondary alcohols could be obtained in high yield with good to excellent enatioselectivities via one-pot sequential hydration/asymmetric transfer hydrogenation (ATH) from terminal alkynes by the combination of of [(IPr)AuCl] and Cp*RhCl[(R,R)-TsDPEN] (Cp* = pentamethylcyclopentadienyl, TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine). Notably, this research exhibited the potential of the direct use of neutral gold(I) complexes instead of cationic ones as catalysts for the activation of multiple bonds for organic synthesis.

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Section: ■ Conclusionmentioning

confidence: 99%

Regioselective Hydration of Terminal Alkynes Catalyzed by a Neutral Gold(I) Complex [(IPr)AuCl] and One-Pot Synthesis of Optically Active Secondary Alcohols from Terminal Alkynes by the Combination of [(IPr)AuCl] and Cp*RhCl[(R,R)-TsDPEN]

Wang

Liu

et al. 2015

J. Org. Chem.

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“…We report herein the allylation of Pd(TPPTS) 3 with allylic alcohols in water into the ionic compounds [Pd(η 3 -alkenyl)(TPPTS) 2 ] + and the allylic phosphonium salts of TPPTS . The study of the stabilityversus pH and temperatureof ionic compounds obtained from allyl alcohol was carried out and provided essential results for a better understanding of catalytic reactions in water with palladium and TPPTS.…”

Section: Introductionmentioning

confidence: 99%

Heterolytic Splitting of Allylic Alcohols with Palladium(0)−TPPTS in Water. Stabilities of the Allylphosphonium Salt of TPPTS and of the Ionic Complex [Pd(η³-allyl)(TPPTS)₂]⁺

et al. 2008

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The Pd(TPPTS)3 complex (TPPTS is the sodium salt of tris(m-sulfophenyl)phosphine) easily ionizes allyl alcohol in water over a wide range of pH: OH− and TPPTS are released, and [Pd(η3-allyl)(TPPTS)2]+ is formed. The released TPPTS further reacts with the palladium cationic complex to reversibly produce both the allylphosphonium salt of TPPTS [(allyl)Ar3P]+ and Pd(TPPTS)3, the latter acting as the catalyst of the allylation of TPPTS by allyl alcohol. Primary allylic alcohols, such as butenol (trans-2-buten-1-ol), prenol (3-methyl-2-buten-1-ol), geraniol, and cinnamyl alcohol, react with Pd(TPPTS)3 to produce hydroxide ion, the corresponding hydrosoluble cationic palladium complex, and allylic phosphonium salts. At room temperature, [Pd(η3-allyl)(TPPTS)2]+ is stable up to pH 12, but beyond this value, palladium precipitates. The temperature has an adverse effect on the complex stability: palladium precipitates at 80 °C, even at pH 7, with the formation of a small amount of propylene. The addition of [(allyl)Ar3P]+ increases the stability of [Pd(η3-allyl)(TPPTS)2]+. Above pH 10, [(allyl)Ar3P]+ decomposes into OTPPTS and propylene by reaction with OH−. At lower pH, [(allyl)Ar3P]+ is slowly isomerized into [(propenyl)Ar3P]+, which further reduces its stability toward pH and temperature. These consecutive reactions of the TPPTS ligand could explain most of the catalyst instability. This study outlines the basis for a better understanding of the instability phenomenon of the catalytic system Pd(0)−TPPTS in reactions with allylic intermediates, e.g. the Tsuji−Trost reaction, and in the reaction of dienes in aqueous media in which palladium often precipitates.

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“…' SUMMARY Hydrogen and methanol ligand exchange between (TMP)Rh-OCH 3 (CH 3 OH) (1) and methanol in solution were observed by 1 H NMR (Figures 2, 3). Hydrogen exchange for coordinated …”

Section: Interchange Of the Porphyrin Face Environments In (Tmp)rh-ocmentioning

confidence: 96%

“…The rate constant for methanol ligand exchange between 1 and the solution varies with the solution composition and fluctuates in a manner that parallels the change in the activation energy for methanol diffusion which is a consequence of solution non-ideality from hydrogen bonded clusters. 1 H NMR (Figure 2, aÀc). Merging of the porphyrin mesityl o-CH 3 resonances into a singlet at concentrations of methanol greater than 1.3 M (Figure 2, dÀg) results from dynamic processes which interchange the chemical environments for the two porphyrin faces.…”

Section: ' Introductionmentioning

confidence: 99%

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Hydrogen and Methanol Exchange Processes for (TMP)Rh-OCH₃(CH₃OH) in Binary Solutions of Methanol and Benzene

Sarkar

Wayland

2011

Inorg. Chem.

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Tetramesityl porphinato rhodium(III) methoxide ((TMP)Rh-OCH(3)) binds with methanol in benzene to form a 1:1 methanol complex ((TMP)Rh-OCH(3)(CH(3)OH)) (1). Dynamic processes are observed to occur for the rhodium(III) methoxide methanol complex (1) that involve both hydrogen and methanol exchange. Hydrogen exchange between coordinated methanol and methoxide through methanol in solution results in an interchange of the environments for the non-equivalent porphyrin faces that contain methoxide and methanol ligands. Interchange of the environments of the coordinated methanol and methoxide sites in 1 produces interchange of the inequivalent mesityl o-CH(3) groups, but methanol ligand exchange occurs on one face of the porphyrin and the mesityl o-CH(3) groups remain inequivalent. Rate constants for dynamic processes are evaluated by full line shape analysis for the (1)H NMR of the mesityl o-CH(3) and high field methyl resonances of coordinated methanol and methoxide groups in 1. The rate constant for interchange of the inequivalent porphyrin faces is associated with hydrogen exchange between 1 and methanol in solution and is observed to increase regularly with the increase in the mole fraction of methanol. The rate constant for methanol ligand exchange between 1 and the solution varies with the solution composition and fluctuates in a manner that parallels the change in the activation energy for methanol diffusion which is a consequence of solution non-ideality from hydrogen bonded clusters.

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Formation of [Pt(η³-allyl)(TPPTS)₂]⁺ from Reaction of cis-Pt(Cl)₂(TPPTS)₂ with Alkenols in Water

Cited by 11 publications

References 51 publications

Regioselective Hydration of Terminal Alkynes Catalyzed by a Neutral Gold(I) Complex [(IPr)AuCl] and One-Pot Synthesis of Optically Active Secondary Alcohols from Terminal Alkynes by the Combination of [(IPr)AuCl] and Cp*RhCl[(R,R)-TsDPEN]

Regioselective Hydration of Terminal Alkynes Catalyzed by a Neutral Gold(I) Complex [(IPr)AuCl] and One-Pot Synthesis of Optically Active Secondary Alcohols from Terminal Alkynes by the Combination of [(IPr)AuCl] and Cp*RhCl[(R,R)-TsDPEN]

Heterolytic Splitting of Allylic Alcohols with Palladium(0)−TPPTS in Water. Stabilities of the Allylphosphonium Salt of TPPTS and of the Ionic Complex [Pd(η³-allyl)(TPPTS)₂]⁺

Hydrogen and Methanol Exchange Processes for (TMP)Rh-OCH₃(CH₃OH) in Binary Solutions of Methanol and Benzene

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Formation of [Pt(η3-allyl)(TPPTS)2]+ from Reaction of cis-Pt(Cl)2(TPPTS)2 with Alkenols in Water

Cited by 11 publications

References 51 publications

Regioselective Hydration of Terminal Alkynes Catalyzed by a Neutral Gold(I) Complex [(IPr)AuCl] and One-Pot Synthesis of Optically Active Secondary Alcohols from Terminal Alkynes by the Combination of [(IPr)AuCl] and Cp*RhCl[(R,R)-TsDPEN]

Regioselective Hydration of Terminal Alkynes Catalyzed by a Neutral Gold(I) Complex [(IPr)AuCl] and One-Pot Synthesis of Optically Active Secondary Alcohols from Terminal Alkynes by the Combination of [(IPr)AuCl] and Cp*RhCl[(R,R)-TsDPEN]

Heterolytic Splitting of Allylic Alcohols with Palladium(0)−TPPTS in Water. Stabilities of the Allylphosphonium Salt of TPPTS and of the Ionic Complex [Pd(η3-allyl)(TPPTS)2]+

Hydrogen and Methanol Exchange Processes for (TMP)Rh-OCH3(CH3OH) in Binary Solutions of Methanol and Benzene

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Product

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Formation of [Pt(η³-allyl)(TPPTS)₂]⁺ from Reaction of cis-Pt(Cl)₂(TPPTS)₂ with Alkenols in Water

Heterolytic Splitting of Allylic Alcohols with Palladium(0)−TPPTS in Water. Stabilities of the Allylphosphonium Salt of TPPTS and of the Ionic Complex [Pd(η³-allyl)(TPPTS)₂]⁺

Hydrogen and Methanol Exchange Processes for (TMP)Rh-OCH₃(CH₃OH) in Binary Solutions of Methanol and Benzene