Topic
Aquation
About: Aquation is a research topic. Over the lifetime, 1443 publications have been published within this topic receiving 17507 citations.
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TL;DR: In this paper, the formato and NN-dimethylformamide (DMF) complexes [Cr(NH3)5(O2CH)]2+ and [Cr[NH3]5 (OCHNMe2)]3+ have been prepared and characterized.
Abstract: The formato- and NN-dimethylformamide (DMF) complexes [Cr(NH3)5(O2CH)]2+ and [Cr(NH3)5(OCHNMe2)]3+ have been prepared and characterized. Ion-exchange separation of the aquation products in the case of the formato-complex indicates that ammonia loss features prominantly. With the DMF complex a single process corresponding to aquation of DMF is observed. Kinetic studies give k1= 1.79 × 10–4 s–1 at 50 °C. I = 1.00M(LiClO4),with activation parameters ΔH‡= 20.2 ± 0.5 kcal mol–1 and ΔS‡=–13.5 ± 1.7 cal K–1 mol–1. Aquation of [Cr(NH3)5F]2+ yields [Cr(NH3)5(H2O)]3+(k2) and [Cr(NH3)4(H2O)F]2+(k3) with the latter predominating over the conditions [H+]= 0.01–1.00M investigated. From product analyses and kinetic studies at different [H+] rate constants have been obtained at 50 °C. I = 1.00M(LiClO4). Aquation of fluoride is [H+]-dependent,k2=a+b[H+] with a= 2.1 × 10–6 s–1 and b= 2.9 × 10–6 l mol–1 s–1, while k3 for ammonia loss is independent of [H+], k3= 7.7 × 10–6 s–1.
7 citations
TL;DR: In this article, aqueous RH(NH3)5Cl2+ shows emission and excited state absorption, ESA, decaying with the same lifetime, attributed to the first triplet thexi state, corresponds to an apparent activation energy of 5.4 plus or minus 0.3 kcal/mole.
7 citations
TL;DR: In this paper, the activation volume at normal pressure (ΔV\eweq) and the reaction volume ( ΔV) were obtained for five aquation reactions of the Co(III) complex ion, and they were interpreted as resulting from the counterbalance of the volume increase attributable to the leaving ligand and the volume decrease due to the partial incorporation of one water molecule in the activated complex.
Abstract: The activation volume at normal pressure (ΔV\eweq) and the reaction volume (ΔV) are obtained for five aquation reactions of the Co(III) complex ion. The results are [given as the complex ion, ΔV\eweq/cm3 mol−1 (t/°C), ΔV/cm3 mol−1 (t/°C)]: trans-[Co(en)2NO2Cl]+, 0.1 (15), −10.4(15); cis-[Co(en)2NO2Cl]+, 0.9 (30), −9.3 (25); cis-[Co(bpy)2NO2Cl]+, 2.9 (30), −9.1 (25); cis-[Co(bpy)2NO2Br]+, 11.3 (30), −6.7 (25); cis-[Co(phen)2NO2Br]+, 3.3 (35), −12.5 (30). These magnitudes of ΔV\eweq are interpreted as resulting from the counterbalance of the volume increase attributable to the dissociation of the leaving ligand and the volume decrease due to the partial incorporation of one water molecule in the activated complex.
7 citations
TL;DR: Raman single-crystal spectra are reported for eight hydrates and deuteriates [MCl5(H2O)]2−(M = In or Fe) as mentioned in this paper.
Abstract: Raman single-crystal spectra are reported for eight hydrates and deuteriates [MCl5(H2O)]2–(M = In or Fe). Many fewer lattice modes were found than predicted, but for the anion internal modes factor-group predictions accord well with observation. A complete assignment in terms of anion C4v symmetry is deduced. Deuteriation enabled identification of all skeletal modes associated with oxygen-atom motions. The most unusual feature of the assignments is that π(MCl4) modes come above δ(MCl4) modes. Comparison with single-crystal assignments for [InCl5]2– show that the largest change is in the A1π(InCl4) mode which is raised upon aquation of the complex.
7 citations
TL;DR: In this article, the rate constants for the title and related reactions are remarkably insensitive to changes in Fe-N bonding, i.e. the different contribution from water structuring around the activated complex.
Abstract: Changes in the rate constants and activation parameters of the title reactions, as the state of protonation of the outgoing ligand and cyanides changes, seem to reflect solely changes due to the different charge type, i.e. the different contribution from water structuring around the activated complex. Rate constants for the title and related reactions are remarkably insensitive to changes in Fe–N bonding.
7 citations