The synthesis of a new unsymmetrical PCN ligand bearing tert-butyl groups on the phosphorus atom and isopropyl groups on the nitrogen donor atom is presented. It reacts with the commercially available Ni­(DME)­Br2 precursor to offer the corresponding t‑BuPCNi‑Pr pincer nickel bromide complex 1 together with a paramagnetic species, which was characterized as a tetrahedral nickel complex. Complex 1 reacts with MeMgCl to give the corresponding methyl complex 3. Carboxylation of complex 3 using 4 atm of CO2 gave the PCN nickel acetate complex 4 under mild reaction conditions comparable to those for the corresponding palladium complexes with PCP ligands.

The synthesis and characterization of N-(2-((7-chloroquinolin-4-yl)amino)ethyl)pyrazine-2-carboxamide (<strong>L</strong>), an aminoquinoline – pyrazinamide hybrid, and the complexes (N-(2-((7-chloroquinolin-4-yl)amino)ethyl)pyrazine-2-carboxamide)(cyclopentadienyl) chlorido-rhodium or iridium hexafluorophosphate ([M(<strong>L</strong>)(Cp*)Cl] PF₆; M = Rh, Ir) and the corresponding chlorido salts ([M(<strong>L</strong>)(Cp*) Cl]Cl; M = Rh, Ir) are described. The ligand and the hexafluorophosphate salts of the metal complexes have been evaluated for anti-plasmodial and anti-mycobacterial activity. The rhodium and the iridium complexes were significantly more active against <em>M. tuberculosis</em> than the free ligand. The crystallographically determined molecular structures of complexes (N-(2-((7-chloroquinolin-4-yl)amino)ethyl)pyrazine-2-carboxamide)(cyclopentadienyl)chlororhodium hexafluoro-phosphate and (N-(2-((7-chloroquinolin-4-yl)amino)ethyl)pyrazine-2-carboxamide)(cyclopentadienyl)chloro-iridium chloride are presented.

The kinetics of the bromination of s -dichloroacetone have been studied in aqueous buffer solutions. The reaction is of zero order with respect to bromine and exhibits general catalysis by bases, so that the observed rate is that of the ionization of the ketone. The catalytic effects of four carboxylate anions and of water are closely related to the basic strengths of the catalysts. In relating rates of ionization to the structures of substituted ketones it is neces­sary to correct the observed rates for the degree of hydration of the carbonyl group in aqueous solution. The corrected rates for acetone and its chloro-derivates are discussed in terms of the polar groups which they contain.