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High-Pressure 17O-NMR. Study of Vanadium (II) in Water: A Second Example of an Associative Interchange Mechanism (Ia) for Solvent Exchange on an Octahedral Divalent Transition-Metal Ion

✍ Scribed by Yves Ducommun; Donald Zbinden; André E. Murbach


Publisher
John Wiley and Sons
Year
1982
Tongue
German
Weight
312 KB
Volume
65
Category
Article
ISSN
0018-019X

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✦ Synopsis


Abstract

The water exchange of [V(H~2~O)~6~]Cl~2~ in aqueous solution has been studied as a function of temperature and pressure (up to 250 MPa), by measuring the ^17^O‐FT‐NMR. line‐widths of the free water resonance at 8.13 MHz. The kinetic parameters obtained are K = 87±4 s^−1^, ΔH^*^ = +61.8 ± 0.7 kJ mo1^−1^ and ΔS^*^ = −0.4±1.9 J mol^−1^ K^−1^. A pressure‐independent volume of activation ΔV^*^ = −4.1±0.1 cm^3^ mol^−1^ is obtained, suggesting an associative interchange (I^a^) mechanism for this early divalent metal ion.