Calorimetric studies of the mixing of a series of carboxylic acids and amines have been carried out to measure heat output, which has been compared with their ability to react to form carboxylate ammonium salts and amides. In order to identify which species (salt or H-bonded species) were formed, 1 H NMR studies were also carried out by mixing carboxylic acids and amines in [D 8 ]toluene and monitoring the resulting reactions. These experiments were also compared to DFT computational studies, from which the relative merits of different mechanistic schemes for direct amide for-

Despite the amide formation reaction being one of the key cornerstone reactions in organic chemistry, the direct amide formation is both little used and little explored. Acceptance of the feasibility and general applicability of the reaction depends upon the ability of researchers to bring it into the mainstream by development of: (1) an understanding of the mechanism of the reaction; and (2) the design of catalysts which promote the reaction on a wide range of substrates and under ambient conditions. From the earliest report of the direct amide formation in the 19th century, there have been relatively few reports of mechanistic studies, though it is clear that there is not a simple relationship between ease of direct amide formation and the pK(a) of the carboxylic acid and amine, or whether salt ammonium carboxylate formation is important. Consequently, direct amide formation has historically been run under higher temperature conditions. However, more recently, stoichiometric and catalytic boron compounds have been developed that considerably reduce the reaction temperatures under which direct amide formation will proceed. Limited attempts at mechanistic studies point to the formation of acyloxyborate or boronate species acting essentially as mixed anhydrides, though the exact order of these systems remains to be categorically determined.

Employing co-catalytic zinc reagents facilitates the iron-catalysed Suzuki cross-coupling of tetraarylborates with both benzyl and 2-heteroaryl halides.

The oxidation of 1-(substituted phenylazo)-2-hydroxynaphthalene-6-sulfonate dyes by oxoiron(IV) tetra(2,6-dichloro-3-sulfonatophenyl)porphyrin (OFe IV TDCSPP) in aqueous solution is first-order in the concentration of the dye and of the oxoiron(IV) species over the pH range 6.93-12.68. The pH dependence of the second-order rate constant, k obs , which shows a minimum between pH 8.5 and 9.5, can be simulated using two pH-dependent equilibria [OFe IV TDCSPP(OH 2 )/OFe IV TDCSPP(OH) and dye/dye anion] and the rate constants for three oxidations, dye by OFe IV TDCSPP(OH 2 ) and OFe IV TDCSPP(OH) and dye anion by OFe IV TDCSPP(OH). The fourth combination, the oxidation of the dye anion by OFe IV TDCSPP(OH 2 ), makes an insignificant contribution to the overall rate of reaction. The mechanisms of the three oxidation processes have been studied using Hammett correlations of substituent effects and by comparisons with the oxidations of isomeric 1-aryl-4-hydroxynaphthalenesulfonate dyes, of an O-methylated dye and of a deuterated 1-phenylazo-2-hydroxynaphthalene-6-sulfonate dye, bearing in mind that the dyes in aqueous solution exist as an equilibrium between azo and hydrazone tautomers. In strongly basic solution the dominant reaction is an electron-transfer oxidation between the dye anion and OFe IV TDCSPP(OH) whereas at neutral pH the major reaction is hydrogen atom-abstraction by OFe IV TDCSPP(OH 2 ) from the azo tautomer of the dye. The mechanism at the pH-rate minimum, between OFe IV TDCSPP(OH) and dye, is less clear and alternatives are discussed.