Catalysis of the ethanolysis of aryl methyl phenyl phosphinate esters by alkali metal ions: transition state structures for uncatalyzed and metal ion-catalyzed reactions

2005 ◽  
Vol 3 (8) ◽  
pp. 1468 ◽  
Author(s):  
Ikenna Onyido ◽  
Kendall Albright ◽  
Erwin Buncel
Keyword(s):  
Alkali Metal ◽  
Transition State ◽  
Metal Ions ◽  
Metal Ion ◽  
Alkali Metal Ions ◽  
Catalyzed Reactions ◽  
Aryl Methyl ◽  
Methyl Phenyl ◽  
Transition State Structures

Alkali metal ion catalysis in nucleophilic displacement by ethoxide ion on p-nitrophenyl phenylphosphonate: Evidence for multiple metal ion catalysis

2003 ◽  
Vol 81 (1) ◽  
pp. 53-63 ◽  
Author(s):  
Erwin Buncel ◽  
Ruby Nagelkerke ◽  
Gregory RJ Thatcher
Keyword(s):  
Alkali Metal ◽  
Transition State ◽  
Metal Ions ◽  
Metal Ion ◽  
Alkali Metal Ions ◽  
Phosphoryl Transfer ◽  
Alkali Metal Ion ◽  
Nucleophilic Displacement ◽  
Displacement Reactions ◽  
Metal Ion Catalysis

In continuation of our studies of alkali metal ion catalysis and inhibition at carbon, phosphorus, and sulfur centers, the role of alkali metal ions in nucleophilic displacement reactions of p-nitrophenyl phenylphosphonate (PNPP) has been examined. All alkali metal ions studied acted as catalysts. Alkali metal ions added as inert salts increased the rate while decreased rate resulted on M+ complexation with 18-crown-6 ether. Kinetic analysis indicated the interaction of possibly three potassium ions, four sodium ions, and five lithium ions in the transition state of the reactions of ethoxide with PNPP. Pre-association of the anionic substrate with two metals ions in the ground state gave the best fit to the experimental data of the sodium system. Thus, the study gives evidence of the role of several metal ions in nucleophilic displacement reactions of ethoxide with anionic PNPP, both in the ground state and in the transition state. Molecular modeling of the anionic transition state implies that the size of the monovalent cation and the steric requirement of the pentacoordinate transition state are the primary limitations on the number of cations that can be brought to bear to stabilize the transition state and catalyze nucleophilic substitution at phosphorus. The bearing of the present work on metal ion catalysis in enzyme systems is discussed, in particular enzymes that catalyze phosphoryl transfer, which often employ multiple metal ions. Our results, both kinetic and modeling, reveal the importance of electrostatic stabilization of the transition state for phosphoryl transfer that may be effected by multiple cations, either monovalent metal ions or amino acid residues. The more such cations can be brought into contact with the anionic transition state, the greater the catalysis observed.Key words: alkali metal ion catalysis, nucleophilic displacement at phosphorus, multiple metal ion catalysis, phosphoryl transfer.

Metal ion catalysis in nucleophilic displacement reactions at carbon, phosphorus, and sulfur centers. III. Catalysis vs. inhibition by metal ions in the reaction of p-nitrophenyl benzenesulfonate with ethoxide

1990 ◽  
Vol 68 (10) ◽  
pp. 1846-1858 ◽  
Author(s):  
Marko J. Pregel ◽  
Edward J. Dunn ◽  
Erwin Buncel
Keyword(s):  
Alkali Metal ◽  
Transition State ◽  
Metal Ions ◽  
Ground State ◽  
Rate Constants ◽  
Metal Ion ◽  
Ion Pairs ◽  
Alkali Metal Ions ◽  
Complexing Agent ◽  
Metal Ion Catalysis

The rate of the nucleophilic displacement reaction of p-nitrophenyl benzenesulfonate (1) with alkali metal ethoxides in ethanol at 25 °C has been studied by spectrophotometric techniques. For lithium ethoxide, sodium ethoxide, potassium ethoxide, and cesium ethoxide, the observed rate constants increase in the order LiOEt < NaOEt < CsOEt < KOEt. The effect of added crown ether and cryptand complexing agents was also investigated. Addition of complexing agent to the reaction of KOEt results in the rate decreasing to a minimum value corresponding to the reaction of free ethoxide. Conversely, addition of complexing agent to the reaction of LiOEt results in the rate increasing to a maximum value that is identical to the minimum value seen in the reaction of KOEt in the presence of excess complexing agent. In complementary experiments, alkali metal ions were added in the form of unreactive salts. Addition of a K+ salt to the reaction of KOEt increases the reaction rate, while addition of a Li+ salt to the reaction of LiOEt decreases the rate. The involvement of metal ions in the reaction of 1 is proposed to occur via reactive alkali metal – ethoxide ion pairs. The kinetic data are analyzed in terms of an ion pairing treatment that allows the calculation of second-order rate constants for free ethoxide and metal–ethoxide ion pairs; the rate constants increase in the order LiOEt < EtO−< NaOEt < CsOEt < KOEt. Thus, Li+isaninhibitorofthereactionofethoxidewith1, whiletheothermetalsionsstudiedareallcatalysts. Equilibrium constants for the association of the various metal ions with the transition state are calculated using a thermodynamic cycle, and are compared to association constants in the ground state. Consistent with the observed kinetic results, Li+ is found to stabilize the ground state more than the transition state, while Na+, K+, and Cs+ all stabilize the transition state more than the ground state. The trend in the magnitude of the transition state stabilization is interpreted in terms of interactions of the transition state with bare or solvated metal ions. It is concluded that the transition state for the reaction of 1 with ethoxide forms solvent separated ion pairs with alkali metal ions. Analogous data were available for the reaction of p-nitrophenyl diphenylphosphinate (2) with ethoxides, where Li+, Na+, K+, and Cs+ all function as catalysts, and the results are analyzed as above. In contrast to the sulfonate system, it is proposed that the phosphinate transition state forms contact ion pairs with alkali metal ions. The difference is attributed to a greater localization of negative charge in the phosphinate transition state, leading to stronger interactions with metal ions, which overcome metal ion – solvent interactions. Keywords: nucleophilic substitution at sulfur, alkali metal ion catalysis.

Membrane transport systems. II. Transport of alkali metal ions against their concentration gradients

1981 ◽  
Vol 59 (12) ◽  
pp. 1734-1744 ◽  
Author(s):  
Thomas M. Fyles ◽  
Virginia A. Malik-Diemer ◽  
Dennis M. Whitfield
Keyword(s):  
Alkali Metal ◽  
Metal Ions ◽  
Metal Ion ◽  
Complex Function ◽  
Membrane System ◽  
Ion Concentration ◽  
Transport Systems ◽  
Alkali Metal Ions ◽  
Concentration Gradients ◽  
Membrane Transport Systems

An artificial membrane system based on a series of macrocyclic polyether carriers (crown ethers) is described. Under the influence of a proton gradient the carriers move alkali metal ions from basic to acidic solution through a chloroform membrane phase. Transport occurs against the concentration gradient of the transported ion as a result of a coupled counterflow of protons. Different transport behaviors are observed depending upon the metal ion concentration. At high metal ion concentration the amount transported is a linear function of time; at lower metal ion concentration the amount transported is a complex function of time which may be described as the result of a pair of consecutive first order processes. Effects of metal ion, carrier, and proton concentration on transport rate are considered. The rate increases with increasing metal ion or carrier concentration but is essentially independent of the pH of either aqueous phase. Increased lipophilicity of the carrier also results in a rate increase. Carriers derived from 18-crown-6 transport potassium selectively and all ions more rapidly than 15-crown-5 derivatives which are, however, selective for sodium. The overall efficiency of the system is discussed in terms of competing "leak" reactions, either of cations from the basic phase or of anions from the acidic phase.

scholarly journals Interaction of Cu+ with cytosine and formation of i-motif-like C–M+–C complexes: alkali versus coinage metals

2016 ◽  
Vol 18 (10) ◽  
pp. 7269-7277 ◽  
Author(s):  
Juehan Gao ◽  
Giel Berden ◽  
M. T. Rodgers ◽  
Jos Oomens
Keyword(s):  
Alkali Metal ◽  
Metal Ions ◽  
Metal Ion ◽  
Alkali Metal Ions ◽  
Metal Ion Complexes ◽  
Coinage Metals

Dimeric metal ion complexes of cytosine C–M+–C display divergent coordination motifs for coinage versus alkali metal ions.

Preparation, ion-exchange, and electrochemical behavior of Cs-type manganese oxides with a novel hexagonal-like morphology

2007 ◽  
Vol 22 (9) ◽  
pp. 2437-2447 ◽  
Author(s):  
Zong-Huai Liu ◽  
Liping Kang ◽  
Mingzhu Zhao ◽  
Kenta Ooi
Keyword(s):  
Ion Exchange ◽  
Alkali Metal ◽  
Metal Ions ◽  
Metal Ion ◽  
Manganese Oxides ◽  
Thermal Analyses ◽  
Alkali Metal Ions ◽  
Ph Titration ◽  
High Discharge Capacity ◽  
Treated Sample

Cs-type layered manganese oxide with a novel hexagonal-like morphology (Cs–BirMO) was prepared by a solid-state reaction procedure. The Cs+ extraction and alkali–metal ion insertion reactions were investigated by chemical analyses, x-ray analyses, scanning electron microscopy observation, Fourier transform-infrared spectroscopy, thermogravimetric differential thermal analyses, pH titration, and distribution coefficient (Kd) measurements. A considerable percentage (88%) of Cs+ ions in the interlayer sites were topotactically extracted by acid treatment, accompanied by a slight change of the lattice parameters. Alkali–metal ions could be inserted into the interlayer of the acid-treated sample (H–BirMO), mainly by an ion-exchange mechanism. The pH titration curve of the H–BirMO sample showed a simple monobasic acid toward Li+, Rb+, and Cs+ ions, and dibasic acid behavior toward Na+ and K+ ions. The order of the apparent capacity was K+ > Li+ ≈ Na+ ≈ Rb+ ≈ Cs+ at pH < 6. The Kd study showed the selectivity sequence of K+ > Rb+ > Na+ > Li+ for alkali–metal ions at the range of pH <5; H–BirMO sample showed markedly high selectivity for the adsorption of K+ ions. Preliminary investigations of the electrochemical properties of the Li+-inserted sample Li–BirMO(1M, 6d) showed that the obtained samples had a relatively high discharge capacity of 115 mAh g−1 and excellent layered stability.

Catalytic pathways in the ethanolysis of fenitrothion, an organophosphorothioate pesticide. A dichotomy in the behaviour of crown/cryptand cation complexing agents

2001 ◽  
Vol 79 (2) ◽  
pp. 157-173 ◽  
Author(s):  
Vimal K Balakrishnan ◽  
Julian M Dust ◽  
Gary W vanLoon ◽  
Erwin Buncel
Keyword(s):  
Alkali Metal ◽  
Transition State ◽  
Metal Ions ◽  
Metal Ion ◽  
Alkali Metals ◽  
Rate Coefficients ◽  
Nucleophilic Attack ◽  
Complexing Agents ◽  
Product Analysis ◽  
Aliphatic Carbon

The rates of displacement of 3-methyl-4-nitrophenoxide ion from the pesticide, fenitrothion, by alkali metal ethoxides in anhydrous ethanol were followed spectrophotometrically. Through product analysis experiments, which included 31P NMR and GC-MS, as well as spectrophotometric analysis, three reaction pathways were identified: nucleophilic attack at the phosphorus centre, attack at the aliphatic carbon, and a minor SNAr route ([Formula: see text]7%). Furthermore, a consecutive process was found to occur on the product of attack at the phosphorus centre. For purposes of kinetic treatment, the processes at the aliphatic and aromatic carbon were combined (i.e., the minor SNAr pathway was neglected), and the observed reaction rate constants were dissected into rate coefficients for nucleophilic attack at phosphorus and at aliphatic carbon. Attack at phosphorus was found to be catalyzed by the alkali metal ethoxides in the order KOEt > NaOEt > LiOEt. Catalysis arises from alkali metal ethoxide aggregates in the base solutions used (0–1.8 M); treatment of the system as a mixture of free ethoxide, ion-paired metal ethoxide, and metal ethoxide dimers resulted in a good fit with the kinetic data. An unexpected dichotomy in the kinetic behaviour of complexing agents (e.g., DC-18-crown-6, [2.2.2]cryptand) indicated that the dimers are more reactive than free ethoxide anions, which are in turn more reactive than ion-paired metal ethoxide. The observed relative order of reactivity is explained in the context of the Eisenman theory in which the free energy of association of the metal ion with the rate-determining transition state is largely determined by the solvent reorganization parameter. In contrast with displacement at the phosphorus centre, attack at the aliphatic carbon was not found to be catalyzed by alkali metals. In this case, the free ethoxide anion was more reactive than either the ion-paired metal ethoxide or the dimeric aggregate. The differing effects of alkali metals on the two pathways is ascribed largely to the leaving group pKa. For carbon attack, the pKa value estimated for demethyl fenitrothion, 2.15, is sufficiently low that metal ions are not required to stabilize the rate-determining transition state. In contrast, for phosphorus attack, 3-methyl-4-nitrophenoxide, with a pKa of 7.15, requires stabilization by metal ion interactions. Hence, alkali metal ions catalyze attack at phosphorus, but not attack at the carbon centres.Key words: organophosphorothioate, pesticide, fenitrothion, ethanolysis, alkali metal ethoxide, ion-pair reactivity, dimers, catalysis, competitive pathways.

Metal ion catalysis in nucleophilic displacement reactions at carbon, phosphorus, and sulfur centers. I. Catalysis by metal ions in the reaction of p-nitrophenyl diphenylphosphinate with ethoxide

1989 ◽  
Vol 67 (9) ◽  
pp. 1440-1448 ◽  
Author(s):  
Edward J. Dunn ◽  
Erwin Buncel
Keyword(s):  
Crown Ether ◽  
Alkali Metal ◽  
Transition State ◽  
Metal Ions ◽  
Ground State ◽  
Metal Ion ◽  
Complexing Agents ◽  
Transition State Stabilization ◽  
Nucleophilic Displacement ◽  
Metal Ion Catalysis

The effect of macrocyclic crown ether and cryptand complexing agents on the rate of the nucleophilic displacement reaction of p-nitrophenyl diphenylphosphinate by alkali metal ethoxides in ethanol at 25 °C has been studied by spectrophotometric techniques. For the reactions of potassium ethoxide, sodium ethoxide, and lithium ethoxide, the observed rate constant increased in the order KOEt < NaOEt < LiOEt. Crown ether and cryptand cation-complexing agents have a retarding effect on the rate. Increasing the ratio of complexing agent to base results in a decrease in kobs to a minimum value corresponding to the rate of reaction of free ethoxide ion. In complementary experiments, alkali metal ions were added to these reaction systems in the form of unreactive salts, causing an increase in reaction rate. The kinetic data were analysed in terms of ion-pairing treatments, which allowed evaluation of rate coefficients due to free ethoxide ions and metal ion – ethoxide ion pairs. Possible roles of the metal cations are discussed in terms of ground state and transition state stabilization. Evaluation of the equilibrium constants for association of the metal ion with ground state (Ka) and the transition state (K′a) shows that catalysis occurs as a result of enhanced association between the metal ion and the transition state, with (K′a) values increasing in the order K+ < Na+ < Li+. A model is proposed in which transition state stabilization arises largely from chelation of the solvated metal ion to two charged oxygen centers. This appears to be the first reported instance of catalysis by alkali metal cations in nucleophilic displacement at phosphoryl centers. Keywords: nucleophilic displacement at phosphorus, alkali-metal-ion catalysis.

Confined alkali metal ion in two-dimensional aluminum phosphate promoted activity for condensation of lactic acid to 2,3-pentanedione

2021 ◽  
Author(s):  
Xinli Li ◽  
Ju Zhang ◽  
Yunsheng Dai ◽  
Congming Tang ◽  
Chenglong Yang
Keyword(s):  
Lactic Acid ◽  
Alkali Metal ◽  
Metal Ions ◽  
Metal Ion ◽  
Aluminum Phosphate ◽  
Sustainable Production ◽  
Alkali Metal Ions ◽  
Two Dimensional ◽  
Alkali Metal Ion

The sustainable production of 2,3-pentanedione from bio-lactic acid was investigated over the alkali metal ion intercalated laminar aluminum phosphate. The confined alkali metal ions by the adjacent layers of aluminum...

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