Chemistry conjugate bases

In most biochemical reactions the pH of the medium is close to 7 At this pH car boxylic acids are nearly completely converted to their conjugate bases Thus it is common practice m biological chemistry to specify the derived carboxylate anion rather than the carboxylic acid itself For example we say that glycolysis leads to lactate by way of pyruvate... 

The coordination chemistry of secondary phosphine chalcogenides and their conjugate bases. B. Walther, Coord. Chem. Rev., 1984, 60, 67 (110). 

Bob s research interests and knowledge across chemistry were great. Throughout his career he retained an interest in biomimetic chemistry, specifically the study of metal ion-promoted reactions and reactions of molecules activated by metal ion coordination. His early interests in carbohydrate chemistry inspired him to study metal ion catalysis of both peptide formation and hydrolysis as well as studies in inorganic reaction mechanisms. He was particularly interested in the mechanisms of base-catalyzed hydrolysis within metal complexes and the development of the so-called dissociative conjugate-base (DCB) mechanism for base-catalyzed substitution reactions at inert d6 metal ions such as Co(III). 

A review of recent advances in chromium chemistry (82) supplements earlier comprehensive reviews of kinetics and mechanisms of substitution in chromium(III) complexes (83). This recent review tabulates kinetic parameters for base hydrolysis of some Cr(III) complexes, mentions mechanisms of formation of polynuclear Cr(III) species, and discusses current views on the question of the mechanism(s) of such reactions. It seems that both CB (conjugate base) and SVj2 mechanisms operate, depending on the situation. The important role played by ionpairing in base hydrolysis of macrocyclic complexes of chromium(III) has been stressed. This is evidenced by the observed order, greater... 

Another example of a case where acid-base chemistry competes with cyclization is found in efforts to construct an analog of the Corey lactone [45], The enantiomerically pure unsaturated ester 91 was assembled and subjected to the conditions indicated in Eq. (26). In this instance, dimethyl methylmalonate was used as the proton donor to avoid 1,4-addition of the conjugate base to 91. Cyclization afforded a combined 77% isolated yield of the y-hydroxy ester 92 and the lactone 93 the former could be converted to the lactone in the... 

Despite all of the activity in pyrimidine-based synthesis, only one study has emerged of solid-phase versions of these reactions <2003TL1267, 20030BC1909>. This chemistry was based upon condensation of dicarbonyl compounds with resin-bound pyrimidine-5,6-diamines through a 2-alkylthio link and oxidative cleavage as described in Section 10.18.7.2. The value of alkylthio substituents in the synthesis of complex substituted pterins has also been demonstrated in the synthesis of nucleic acid conjugates <2004OBC3588> (see Section 10.18.12.4). 

In Section 9-3, we considered o- and p-hydroxybenzoic acids, designated HA. Now consider their conjugate bases. For example, the salt sodium o-hydroxybenzoate dissolves to give Na+ (which has no acid-base chemistry) and o-hydroxybenzoate. which is a weak base. The acid-base chemistry is the reaction of o-hydroxybenzoate with water ... 

Equation 2.6 is the familiar Henderson-Hasselbalch equation, which defines the relationship between pH and the ratio of acid and conjugate base concentrations. The Henderson-Hasselbalch equation is of great value in buffer chemistry because it can be used to calculate the pH of a solution if the molar ratio of buffer ions ([A-]/[HA]) and the pKa of HA are known. Also, the molar ratio of HA to A- that is necessary to prepare a buffer solution at a specific pH can be calculated if the pKa is known. 

The organometallic chemistry of alkynylcyclopropanes involves primarily the formation and reactions of carbon-metal er-bonds. Metals come essentially from the main group elements, with lithium playing a major role. The two metallation sites are the cyclopropyl and the acetylenic positions, which are expected to differ considerably in their acidity values (t-butylacetylene, pKa = 25230, cyclopropane, pKa = 46183) but less in the reactivity of their metal conjugated bases towards electrophiles. 

Further chemistry of alkenes and alkynes is described in this chapter, with emphasis on addition reactions that lead to reduction and oxidation of carbon-carbon multiple bonds. First we explain what is meant by the terms reduction and oxidation as applied to carbon compounds. Then we emphasize hydrogenation, which is reduction through addition of hydrogen, and oxidative addition reactions with reagents such as ozone, peroxides, permanganate, and osmium tetroxide. We conclude with a section on the special nature of 1-alkynes— their acidic behavior and how the conjugate bases of alkynes can be used in synthesis to form carbon-carbon bonds. 

Theory helps the experimentalists in many ways this volume is on chemical shift calculations, but the other ways in which theoretical chemistry guides NMR studies of catalysis should not be overlooked. Indeed, further theoretical work on two of the cations discussed above has helped us understand why some carbenium ions persist indefinitely in zeolite solid acids as stable species at 298 K, and others do not (25). The three classes of carbenium ions we were most concerned with, the indanyl cation, the dimethylcyclopentenyl cation, and the pentamethylbenzenium cation (Scheme 1), could all be formally generated by protonation of an olefin. We actually synthesized them in the zeolites by other routes, but we suspected that the simplest parent olefins" of these cations must be very basic hydrocarbons, otherwise the carbenium ions might just transfer protons back to the conjugate base site on the zeolite. Experimental values were not available for any of the parent olefins shown below, so we calculated the proton affinities (enthalpies) by first determining the... 

A subtle, but important, point must be made before we can extend our understanding of acid-base chemistry to the reaction between a Grignard or alkyllithium reagent and a carbonyl group. The data in the table of Br /nsted acids and their conjugate bases reflect the strengths of common acids and bases when they act as Brif/nstedacids or bases. These data predict that methyllithium should react with acetylene to form methane and an acetylide ion, for example. 

For most aqueous acid-base chemistry, the Lewis definitions are too general and lack the symmetry of the acid-conjugate base relationship. We will mostly use the Bronsted-Lowry definitions. 

George Olah published a perspective in which he provided an overview of the research of his group over five decades.1 Christopher Reed surveyed the chemistry of carborane acids, the strongest pure Brpnsted acids known, with a conjugate base that engages in little chemistry.2 These acids are employed to prepare highly acidic carbocations, including protonated benzene, protonated C6o, tertiary carbocations, vinyl cations, and silylium ions. The synthesis and properties of unusual... 

Now we are ready to examine another great rule of thumb in chemistry. The stronger the acid, the weaker its conjugate base. For example, let s take a close look at carbonic acid. 

Well, in case you hadn t noticed, sodium ions don t seem to do much in chemistry. They are almost always spectator ions, because they don t participate in any of the chemical reactions. Their job is to provide a charge balance to the anions in solution. So, in calculating the pH of sodium acetate, we ignore sodium. The acetate ion, however, is the conjugate base of the weak acid, acetic acid. Therefore, the acetate ion is a base, and we can write this ionization equilibrium equation. 

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