𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Ligand-Exchange Processes on Solvated Lithium Cations: DMSO and Water/DMSO Mixtures

✍ Scribed by Ewa Pasgreta; Ralph Puchta; Michael Galle; Nico van Eikema Hommes; Achim Zahl; Rudi van Eldik

Publisher
John Wiley and Sons
Year
2007
Tongue
English
Weight
247 KB
Volume
8
Category
Article
ISSN
1439-4235

No coin nor oath required. For personal study only.

✦ Synopsis

Abstract

Solutions of LiClO~4~ in solvent mixtures consisting of dimethylsulfoxide (DMSO) and water, or DMSO and γ‐butyrolactone, were studied by ^7^Li NMR spectroscopy (for complexation by cryptands in γ‐butyrolactone as a solvent, see: E. Pasgreta, R. Puchta, M. Galle, N. J. R. van Eikema Hommes, A. Zahl, R. van Eldik, J. Incl. Phen., 2007, 58, 81–88). Chemical shifts indicate that the Li^+^ ion is coordinated by four DMSO molecules. In the binary solvent mixture of water and DMSO, no selective solvation is detected, thus indicating that on increasing the water content of the solvent mixture, DMSO is gradually displaced by water in the coordination sphere of Li^+^. The ligand‐exchange mechanism of Li^+^ ions solvated by DMSO and water/DMSO mixtures was studied using DFT calculations. Ligand exchange on [Li(DMSO)~4~]^+^ was found to follow a limiting associative (A) mechanism. The displacement of coordinated H~2~O by DMSO in [Li(H~2~O)~4~]^+^ follows an associative interchange mechanism. The suggested mechanisms are discussed in reference to available experimental and theoretical data.

📜 SIMILAR VOLUMES

Ligand Exchange Processes on Solvated Li
Ligand Exchange Processes on Solvated Lithium Cations: Complexation by Cryptands in Acetone as Solvent
✍ Ewa Pasgreta; Ralph Puchta; Achim Zahl; Rudi van Eldik 📂 Article 📅 2007 🏛 John Wiley and Sons 🌐 English ⚖ 248 KB

## Abstract Kinetic studies on Li^+^ exchange between the cryptands C222 and C221 and acetone as solvent were performed as a function of ligand‐to‐metal ratio, temperature and pressure using ^7^Li NMR spectroscopy. Temperature and pressure dependence measurements were performed in the presence of a

Evidence for Interchange Ligand-Exchange
Evidence for Interchange Ligand-Exchange Processes on Solvated Beryllium Cations
✍ Ralph Puchta; Nico van Eikema Hommes; Rudi van Eldik 📂 Article 📅 2005 🏛 John Wiley and Sons 🌐 German ⚖ 284 KB

## Abstract The ligand‐exchange mechanism of solvated Be^2+^ cations has been studied by means of DFT calculations (RB3LYP/6‐311+G\*\*). Ligand exchange around [BeL~4~]^2+^, where L=H~2~O, NH~3~, CO~2~, formaldehyde (H~2~CO), HCN, N~2~, and CO, was found to follow an associative interchange (I~a~)

Ligand-Exchange Processes on Solvated Be
Ligand-Exchange Processes on Solvated Beryllium Cations. Part III : Which Model Reaction is Preferable for Quantum-Chemical Investigations of a Water-Exchange Mechanism?
✍ Ralph Puchta; Rudi van Eldik 📂 Article 📅 2008 🏛 John Wiley and Sons 🌐 German ⚖ 314 KB

On the basis of DFT calculations (B3LYP/6-311 þ G\*\*), the possibility to include solvent effects is considered in the investigation of the H 2 O-exchange mechanism on [Be(H 2 O) 4 ] 2þ within the widely used cluster approach. The smallest system in the gas phase, [Be(H 2 O) 4 (H 2 O)] 2þ , shows t