Ligand Substitution Reactions at Inorganic Centers

Richens, David T.

doi:10.1021/cr030705u

Cited by 306 publications

(307 citation statements)

References 270 publications

(452 reference statements)

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“…The ratio of k 1OH /k 0 0 is ca. 140, which is consistent with typical values for hydroxo and aqua chromium(III) complexes [23]. This reactivity difference is obviously a result of labilizing effect of hydroxo ligands.…”

Section: (O-gly)(oh)]supporting

confidence: 86%

Kinetic studies on chromium-glycinato complexes in acidic and alkaline media

Kita

Marai

Muzioł

et al. 2010

Transition Met Chem

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], where k 0 and k 1 are rate constants for the chelate-ring opening via spontaneous and acid-catalysed reaction paths, respectively, and K p1 is the protonation constant. The proposed mechanism assumes formation of the reactive intermediate as a result of proton addition to the coordinated carboxylate group of the didentate ligand. Some kinetic studies on the second reaction stage, the one-end bonded glycine liberation, were also done. The obtained results were analogous to those for stage I. In this case, the proposed reactive species are intermediates, protonated at the carboxylate group of the monodentate glycine.

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Section: (O-gly)(oh)]supporting

confidence: 86%

Kinetic studies on chromium-glycinato complexes in acidic and alkaline media

Kita

Marai

Muzioł

et al. 2010

Transition Met Chem

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“…III oligomers: From work on small ions, it is clear that the first step in dissociation is protonation, which is usually much faster ( % 10 À9 -10 À4 s) than the subsequent bridging-bond ruptures, so that the relative fraction of m 2 -OH 2 and m 2 -OH is controlled by the solution pH [55,[60][61][62] (see Tables S-3 and S-4, in the Supporting Information). The second step is hydration by another incoming water molecule leading to dissociation of the bridge, sometimes via an m 2 -H 3 O 2 À moiety.…”

Section: Dissociation Of Crmentioning

confidence: 99%

Minerals as Molecules—Use of Aqueous Oxide and Hydroxide Clusters to Understand Geochemical Reactions

Casey

Rustad

Spiccia

2009

Chemistry A European J

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Large aqueous oxide ions as minerals! Minerals dissolve by repeated ligand exchange reactions and geochemists use polyoxometalate ions to establish structure-reactivity relations for environmentally important functional groups. Here, for example, are plotted the dissolution rates of two classes of minerals against rates of solvent exchanges around the corresponding aquo ions.Geochemists and environmental chemists make predictions about the fate of chemicals in the shallow earth over enormously long times. Key to these predictions is an understanding of the hydrolytic and complexation reactions at oxide mineral surfaces that are difficult to probe spectroscopically. These minerals are usually oxides with repeated structural motifs, like silicate or aluminosilicate polymers, and they expose a relatively simple set of functional groups to solution. The geochemical community is at the forefront of efforts to describe the surface reactivities of these interfacial functional groups and some insights are being acquired by using small oligomeric oxide molecules as experimental models. These small nanometer-size clusters are not minerals, but their solution structures and properties are better resolved than for minerals and calculations are relatively well constrained. The primary experimental data are simple rates of steady oxygen-isotope exchanges into the structures as a function of solution composition that can be related to theoretical results. There are only a few classes of large oxide ions for which data have been acquired and here we review examples and illustrate the general approach, which also derives directly from the use of model clusters to understand for the active core of metalloenzymes in biochemistry.

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“…Generally, coordination compounds of this type play important roles in the activity of metalloenzymes or during transport processes of metal ions across cell membranes [14]. The [Co(en) 2 Cl 2 ]Cl complex seems to be especially interesting since the biological tests were carried out with its participation.…”

Section: Introductionmentioning

confidence: 99%

Thermal properties of [Co(en)2Cl2]Cl in solid state. Cis–trans isomerization of the [Co(en)2Cl2]+ complex ion in methanol

Jacewicz

Pranczk

Wyrzykowski

et al. 2014

Reac Kinet Mech Cat

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]Cl complex isomers have been studied using the TG-FTIR and TG-DSC-MS techniques. The measurements were carried out in argon atmosphere over the temperature range 293-873 K. The influence of the configurational geometry on the pathways of thermal transformations was discussed. Furthermore, kinetic studies on the reaction of the cis-trans isomerization of the [Co(en) 2 Cl 2 ]Cl complex salt in methanolic solutions were performed using UV-Vis spectrophotometry at five temperatures in the 293-313 K temperature range. The observed rate constants were computed using the ''Glint'' program based on the global analysis. It has been found that the cis-trans isomerization of [Co(en) 2 Cl 2 ]Cl is a first order reaction. Furthermore, the cis/trans [Co(en) 2 Cl 2 ]Cl isomerization proceeds according to the dissociative mechanism.

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Ligand Substitution Reactions at Inorganic Centers

Cited by 306 publications

References 270 publications

Kinetic studies on chromium-glycinato complexes in acidic and alkaline media

Kinetic studies on chromium-glycinato complexes in acidic and alkaline media

Minerals as Molecules—Use of Aqueous Oxide and Hydroxide Clusters to Understand Geochemical Reactions

Thermal properties of [Co(en)2Cl2]Cl in solid state. Cis–trans isomerization of the [Co(en)2Cl2]+ complex ion in methanol

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