Douglas X. West

Metal ion complexes of 2-pyridylcarbinol N-oxide

Abstract Transition metal ion complexes of the potentially bidentate ligand 2-pyridylcarbinol N-oxide have been prepared. They are characterized and identified by chemical analysis and physical measurements. Their IR and electronic spectra are discussed with regard to monodentate or bidentate bonding of the ligand. The Cr(III) and Fe(III) complexes each contain two 2-pyridylcarbinol N-oxide ligands and a conjugate base of the carbinol in their coordination spheres. The remaining metal ions crystallized with either four (Mn(II), Ni(II), Cu(II), Zn(II)) or six (Co(II)) neutral ligands.

Oxygen-18 exchange between enriched water and pentacyanonitroferrate(II) ion

Abstract The rate of exchange of oxygen-18 between sodium pentacyanonitroferrate(II) and enriched water was studied. The effects on the rate of exchange caused by changes in concentration of Na4Fe(CN)5NO2, pH of the solution, ionic strength of the solution, and the solutions temperature were studied. The proposed mechanism is Fe(CN) 5 NO 2 -4 + H 2 O ⇌ k -1 k 1 Fe(CN) 5 NO 2 H -3 + OH - Fe(CN) 5 NO 2 H -3 + H 2 O ⇌ k -2 k 2 Fe(CN) 5 NO 2 + H 2 -2 + OH - Fe(CN) 5 NO 2 H -3 + O∗H - → k 3 Fe(CN) 5 NOO∗H -3 + OH - and the rate law for oxygen-18 exchange is Rate = k 3 ( k 1 [ Fe(CN) 5 NO 2 -4 ]+ k -2 [ Fe(CN) 5 NO 2 H 2 -2 ][ OH - ]) k -1 [ OH - + k 2 The activation energy is 15·4±0·5 kcal/mole.

Kinetics of the reaction between photolyzed sodium pentacyanonitrosylferrate(II) and sodium thiocyanate

Abstract The reaction of monochromatically photolyzed aqueous Fe(CN) 5 NO 2− solutions with thiocyanate ion has been found to yield the blue iron(III) complex Fe(CN) 5 SCN 3− , and nitric oxide. The rate determining step involves the formation of pentacyanothiocyanatoferrate(II) which is then rapidly oxidized by nitrite ion or nitrous acid to the final product. Concentrations of thiocyanate ion, pH and temperature were varied in determining the rate law.

Reactions of sodium pentacyanonitrosylferrate(II) with some thioureas in methanol solution

Abstract The kinetics of the reaction between photolysed sodium pentacyanonitrosylferrate(II) and some thioureas in methanol solution are reported. The reactions are first order in both complex ion and thiourea. A mechanism is proposed and the activation parameters are reported.

Reaction between thiourea and alkaline solutions of sodium pentacyanonitrosylferrate(II)

Abstract The kinetics and mechanism of the reaction between thiourea and basic solutions of sodium pentacyanonitrosylferrate(II) are reported. The product of the reaction is a violet powder having a molecular formula of Na 5 Fe 2 C 9 N 12 SH 8 O 5 .

Solvent effects on the acid-catalyzed hydrolysis of tetramethylurea

Tetramethylurea was hydrolyzed in aqueous hydrochloric acid at temperatures of 80, 90, and 100°C. All reactions were carried out in an excess of both tetramethylurea and water, with first-order dependence on acid concentration being observed. As the concentration of water was increased, the rate of hydrolysis decreased until equimolar amounts of water and tetramethylurea were present. Subsequent addition of water had no effect on the observed rate.