Kinetics of CO Addition to Ni(cyclam)+ in Aqueous Solution
Inorganic Chemistry1996Vol. 35(18), pp. 5122–5126
Citations Over TimeTop 10% of 1996 papers
Abstract
The addition of CO to Ni(cyclam)+ in homogeneous aqueous solution has been studied by pulse radiolysis and laser flash photolysis. The reaction was found to proceed by a sequential, two-step mechanism. The CO addition rate constant was found to be (2.0 ± 0.2) × 109 M-1 s-1 at ambient temperature. Addition is followed by a slower, first-order reaction with a rate constant of 1.8 ± 0.2 s-1 at ambient temperature. A variable temperature study of the latter reaction yielded ΔH⧧ = 12.7 ± 0.1 kcal mol-1 and ΔS⧧ = −14.4 ± 0.1 cal K-1 mol-1. The mechanism of the reaction sequence and the possibility that the slow, first-order process represents an isomerization of the macrocyclic ligand are discussed.
Related Papers
- → A pulse radiolysis and flash photolysis study of the radicals SO-2, SO-3, SO-4 and SO-5(1989)51 cited
- → Syntheses, structures and bonding of 3d metal alkynyl complexes of cyclam and its derivatives(2019)23 cited
- → Study of M(iii)-cyclam (M = Rh, Ru; cyclam = 1,4,8,11-tetraazacyclotetradecane) complexes as novel methanol resistant electrocatalysts for the oxygen reduction reaction(2020)14 cited
- → Effects of Steric Constraint on Chromium(III) Complexes of Tetraazamacrocycles, 2. Comparison of the Chemistry and Photobehavior of the trans-Dichloro- and trans-Dicyano- Complexes of Cyclam, 1,4-C2-Cyclam, and 1,11-C3-Cyclam(2005)20 cited
- → Magnetostructural examination of Mn(III) complexes [Mn(cyclam)X2]+ with strong axial ligands(2009)5 cited