Abstract
The rate of water exchange on Ru(NH3)5OH2 3+ in aqueous CF3SO3H (0.01 mol L-1) is characterized by k298.2 = 2.30 × 10-4 s-1, ΔH* = 91.5 kJ mol-1, ΔS* = -7.7 J K-1 mol-1, and ΔV* = -4.0 cm3 mol-1. The order of lability of M(NH3)5OH2 3+ in water exchange is (M=) Ru > Cr > Rh > Co ≫ Ir and is governed by ΔH*. For substitution reactions of metal complexes involving "hard" leaving groups, the lability sequence first < second > third transition series may be general. For a series of related aqua complexes such as M(NH3)5OH2 3+, variations in ΔV* for water exchange and the molar volume of the complex as M is changed are largely compensatory, so that the molar volume of the transition state varies relatively little. This reflects reduced accessibility of the complex to associative attack as the central ion becomes smaller.
| Original language | English |
|---|---|
| Pages (from-to) | 3240-3242 |
| Number of pages | 3 |
| Journal | Inorganic Chemistry |
| Volume | 26 |
| Issue number | 20 |
| Publication status | Published - 1987 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
Transition-state volumes in solvent exchange. Water exchange on the aqueous aquapentaammineruthenium(III) ion. / Doine, Hideo; Ishihara, Koji; Krouse, H. Roy; Swaddle, Thomas W.
In: Inorganic Chemistry, Vol. 26, No. 20, 1987, p. 3240-3242.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Transition-state volumes in solvent exchange. Water exchange on the aqueous aquapentaammineruthenium(III) ion
AU - Doine, Hideo
AU - Ishihara, Koji
AU - Krouse, H. Roy
AU - Swaddle, Thomas W.
PY - 1987
Y1 - 1987
N2 - The rate of water exchange on Ru(NH3)5OH2 3+ in aqueous CF3SO3H (0.01 mol L-1) is characterized by k298.2 = 2.30 × 10-4 s-1, ΔH* = 91.5 kJ mol-1, ΔS* = -7.7 J K-1 mol-1, and ΔV* = -4.0 cm3 mol-1. The order of lability of M(NH3)5OH2 3+ in water exchange is (M=) Ru > Cr > Rh > Co ≫ Ir and is governed by ΔH*. For substitution reactions of metal complexes involving "hard" leaving groups, the lability sequence first < second > third transition series may be general. For a series of related aqua complexes such as M(NH3)5OH2 3+, variations in ΔV* for water exchange and the molar volume of the complex as M is changed are largely compensatory, so that the molar volume of the transition state varies relatively little. This reflects reduced accessibility of the complex to associative attack as the central ion becomes smaller.
AB - The rate of water exchange on Ru(NH3)5OH2 3+ in aqueous CF3SO3H (0.01 mol L-1) is characterized by k298.2 = 2.30 × 10-4 s-1, ΔH* = 91.5 kJ mol-1, ΔS* = -7.7 J K-1 mol-1, and ΔV* = -4.0 cm3 mol-1. The order of lability of M(NH3)5OH2 3+ in water exchange is (M=) Ru > Cr > Rh > Co ≫ Ir and is governed by ΔH*. For substitution reactions of metal complexes involving "hard" leaving groups, the lability sequence first < second > third transition series may be general. For a series of related aqua complexes such as M(NH3)5OH2 3+, variations in ΔV* for water exchange and the molar volume of the complex as M is changed are largely compensatory, so that the molar volume of the transition state varies relatively little. This reflects reduced accessibility of the complex to associative attack as the central ion becomes smaller.
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M3 - Article
VL - 26
SP - 3240
EP - 3242
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 20
ER -