Multi-mechanism linear free energy relationships and isoequilibrium or isokinetic temperatures

Bunten, Kevin A.; Poë, Anthony J.

doi:10.1039/b603023h

Cited by 12 publications

(4 citation statements)

References 45 publications

(89 reference statements)

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“…Although comparison of the three studied processes has to be done with caution due to the different solvent and slightly different temperature range used in the analysis of the Py and DAD complexes, we observed a linear compensation effect when plotting values of Δ H ⧧ versus Δ S ⧧ for the three processes, which would further support the same type of mechanism along the series (see the SI for details) …”

Section: Results and Discussionmentioning

confidence: 43%

Twists and Turns of Platinum-Allene Complexes: NMR Techniques for the Study of the Dynamic Behavior in Solution

et al. 2016

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Classic (dynamic exchange line-shape analysis) and novel (SSTD NMR) NMR techniques have been applied in order to obtain the kinetic and thermodynamic parameters of the three main processes occurring in the fluxional behavior of Pt-allene complexes with N-containing ligands, in four and five coordination mode, in solution. Our results show intramolecular helical and rotational movements closely related to each other, confirming η 1 -staggered structures as possible intermediates. The ligand exchange in these complexes seems to occur via a ligand-independent dissociative mechanism, where coordinating solvents might be involved in the stabilization of the intermediates. The differences observed in the interaction of allenes with other metals could be the basis to explain the divergent reactivity observed in platinum-catalyzed processes.

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Section: Results and Discussionmentioning

confidence: 43%

Twists and Turns of Platinum-Allene Complexes: NMR Techniques for the Study of the Dynamic Behavior in Solution

et al. 2016

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“…The application of linear Gibbs energy relationships, most notably the Hammett equation, was found to be very powerful in interpreting the reversible and irreversible potentials of classes of compounds as a function of the substituents on the molecule. The early work is summarized in the monograph by Zuman 11 and the subject continues to be the topic of additional applications and refinements [12][13][14][15][16][17][18][19][20][21] as well as reviews. 22 Early applications of theory were based on the Hu ¨ckel molecular orbital theory and extensions.…”

Section: Correlations With Molecular Propertiesmentioning

confidence: 99%

One-Electron and Two-Electron Transfers in Electrochemistry and Homogeneous Solution Reactions

2008

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“…The resultant parameters capturing ligand properties, also called ligand descriptors, can aid the interpretation of experimental results. Thus the analysis of correlations or the fitting of simple regression models can highlight the relationship between a given observable and a small number of descriptors . Ligand descriptors can also be used to select ligands for experimentation, either by choosing a selection of ligands to achieve a chemically varied test set , or by highlighting subsets of ligands whose complexes have desirable properties, such as high catalytic activity, in common and thus focusing further study on “hot spots” within the ligand space. ,,− Where suitable experimental training data are available, i.e., those sampling a varied ligand set under the same reaction conditions and capturing a good range of response data, such descriptors can be used to derive regression models suitable for making predictions about other ligands; these models often require more extensive descriptor databases, and detailed chemical interpretation becomes more difficult.…”

Section: Introductionmentioning

confidence: 99%

Expansion of the Ligand Knowledge Base for Monodentate P-Donor Ligands (LKB-P)

Jover¹,

Fey²,

Harvey³

et al. 2010

Organometallics

131

164

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We have expanded the ligand knowledge base for monodentate P-donor ligands (LKB-P, Chem. Eur. J. 2006, 12, 291-302) by 287 ligands and added descriptors derived from computational results on a gold complex [AuClL]. This expansion to 348 ligands captures known ligand space for this class of monodentate two-electron donor ligands well, and we have used principal component analysis (PCA) of the descriptors to derive an improved map of ligand space. Potential applications of this map, including the visualization of ligand similarities/differences and trends in experimental data, as well as the design of ligand test sets for high-throughput screening and the identification of ligands for reaction optimization, are discussed. Descriptors of ligand properties can also be used in regression models for the interpretation and prediction of available response data, and here we explore such models for both experimental and calculated data, highlighting the advantages of large training sets that sample ligand space well. † Development of a Ligand Knowledge Base, Part 6. See refs 1-5 for Parts 1-5.

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Multi-mechanism linear free energy relationships and isoequilibrium or isokinetic temperatures

Cited by 12 publications

References 45 publications

Twists and Turns of Platinum-Allene Complexes: NMR Techniques for the Study of the Dynamic Behavior in Solution

Twists and Turns of Platinum-Allene Complexes: NMR Techniques for the Study of the Dynamic Behavior in Solution

One-Electron and Two-Electron Transfers in Electrochemistry and Homogeneous Solution Reactions

Expansion of the Ligand Knowledge Base for Monodentate P-Donor Ligands (LKB-P)

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