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Water Exchange Mechanism of Tetraaquapalladium(II). A Variable Pressure and Variable Temperature Oxygen-217 NMR Study

Helm, Lothar; Elding, Lars Ivar LU and Merbach, Andre E. (1984) In Helvetica Chimica Acta 67(6). p.1453-1460
Abstract (Swedish)
Water exchange of square-planar Pd(H2O)42+ has been studied as a function of temperature (240 to 345 K) and pressure (0.1 to 260 MPa, at 324 K) by measuring the 17/O-FT-NMR line-widths of the resonance from coordinated water at 27.11 and 48.78 MHz. The following exchange parameters were obtained: k298ex = (560 ± 40) s−1, ΔH* = (49.5 ± 1.9) kJ mol−1, ΔS* = – (26 ± 6) J K−1 mol−1 and ΔV* = – (2.2 ± 0.2) cm3 mol−1. The values refer to an aqueous perchlorate medium with an ionic strength between 2.0 and 2.6 m and a perchloric-acid concentration between 0.8 and 1.7 m, and are interpreted in terms of an associative (a) activation for the exchange. The exchange rate for Pd(H2O)42+ is 1.4 × 106 times faster than for Pt(H2O)42+ at 298 K. A... (More)
Water exchange of square-planar Pd(H2O)42+ has been studied as a function of temperature (240 to 345 K) and pressure (0.1 to 260 MPa, at 324 K) by measuring the 17/O-FT-NMR line-widths of the resonance from coordinated water at 27.11 and 48.78 MHz. The following exchange parameters were obtained: k298ex = (560 ± 40) s−1, ΔH* = (49.5 ± 1.9) kJ mol−1, ΔS* = – (26 ± 6) J K−1 mol−1 and ΔV* = – (2.2 ± 0.2) cm3 mol−1. The values refer to an aqueous perchlorate medium with an ionic strength between 2.0 and 2.6 m and a perchloric-acid concentration between 0.8 and 1.7 m, and are interpreted in terms of an associative (a) activation for the exchange. The exchange rate for Pd(H2O)42+ is 1.4 × 106 times faster than for Pt(H2O)42+ at 298 K. A comparison with reactions between other nucleophiles and Pd(H2O)42+ is also made. (Less)
Abstract
Water exchange of square-planar Pd(H2O)42+ has been studied as a function of temperature (240 to 345 K) and pressure (0.1 to 260 MPa, at 324 K) by measuring the 17/O-FT-NMR line-widths of the resonance from coordinated water at 27.11 and 48.78 MHz. The following exchange parameters were obtained: k298ex = (560 ± 40) s−1, ΔH* = (49.5 ± 1.9) kJ mol−1, ΔS* = – (26 ± 6) J K−1 mol−1 and ΔV* = – (2.2 ± 0.2) cm3 mol−1. The values refer to an aqueous perchlorate medium with an ionic strength between 2.0 and 2.6 m and a perchloric acid concentration between 0.8 and 1.7 m, and are interpreted in terms of an associative (a) activation for the exchange. The exchange rate for Pd(H2O)42+ is 1.4 × 106 times faster than for Pt(H2O)42+ at 298 K. A... (More)
Water exchange of square-planar Pd(H2O)42+ has been studied as a function of temperature (240 to 345 K) and pressure (0.1 to 260 MPa, at 324 K) by measuring the 17/O-FT-NMR line-widths of the resonance from coordinated water at 27.11 and 48.78 MHz. The following exchange parameters were obtained: k298ex = (560 ± 40) s−1, ΔH* = (49.5 ± 1.9) kJ mol−1, ΔS* = – (26 ± 6) J K−1 mol−1 and ΔV* = – (2.2 ± 0.2) cm3 mol−1. The values refer to an aqueous perchlorate medium with an ionic strength between 2.0 and 2.6 m and a perchloric acid concentration between 0.8 and 1.7 m, and are interpreted in terms of an associative (a) activation for the exchange. The exchange rate for Pd(H2O)42+ is 1.4 × 106 times faster than for Pt(H2O)42+ at 298 K. A comparison with reactions between other nucleophiles and Pd(H2O)42+ is also made. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Palladium(II), Tetraaqua complex, Water exchange, Stopped-flow kinetics, High-pressure stopped flow, Reaction mechanism, Activation volume, Activation entropy, Associative process
in
Helvetica Chimica Acta
volume
67
issue
6
pages
8 pages
publisher
John Wiley & Sons
external identifiers
  • scopus:3042716135
ISSN
0018-019X
DOI
10.1002/hlca.19840670605
language
English
LU publication?
yes
id
1cfcbd02-e541-4bb0-8bb1-0a4d6eabb3f6
date added to LUP
2017-02-06 17:59:26
date last changed
2017-08-20 05:07:39
@article{1cfcbd02-e541-4bb0-8bb1-0a4d6eabb3f6,
  abstract     = {Water exchange of square-planar Pd(H2O)42+ has been studied as a function of temperature (240 to 345 K) and pressure (0.1 to 260 MPa, at 324 K) by measuring the 17/O-FT-NMR line-widths of the resonance from coordinated water at 27.11 and 48.78 MHz. The following exchange parameters were obtained: k298ex = (560 ± 40) s−1, ΔH* = (49.5 ± 1.9) kJ mol−1, ΔS* = – (26 ± 6) J K−1 mol−1 and ΔV* = – (2.2 ± 0.2) cm3 mol−1. The values refer to an aqueous perchlorate medium with an ionic strength between 2.0 and 2.6 m and a perchloric acid concentration between 0.8 and 1.7 m, and are interpreted in terms of an associative (a) activation for the exchange. The exchange rate for Pd(H2O)42+ is 1.4 × 106 times faster than for Pt(H2O)42+ at 298 K. A comparison with reactions between other nucleophiles and Pd(H2O)42+ is also made.},
  author       = {Helm, Lothar and Elding, Lars Ivar and Merbach, Andre E.},
  issn         = {0018-019X},
  keyword      = {Palladium(II),Tetraaqua complex,Water exchange,Stopped-flow kinetics,High-pressure stopped flow,Reaction mechanism,Activation volume,Activation entropy,Associative process},
  language     = {eng},
  number       = {6},
  pages        = {1453--1460},
  publisher    = {John Wiley & Sons},
  series       = {Helvetica Chimica Acta},
  title        = {Water Exchange Mechanism of Tetraaquapalladium(II). A Variable Pressure and Variable Temperature Oxygen-217 NMR Study},
  url          = {http://dx.doi.org/10.1002/hlca.19840670605},
  volume       = {67},
  year         = {1984},
}