Water Exchange Mechanism of Tetraaquapalladium(II). A Variable Pressure and Variable Temperature Oxygen-217 NMR Study
(1984) In Helvetica Chimica Acta 67(6). p.1453-1460- 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)
- 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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1cfcbd02-e541-4bb0-8bb1-0a4d6eabb3f6
- author
- Helm, Lothar ; Elding, Lars Ivar LU and Merbach, Andre E.
- organization
- publishing date
- 1984-09
- 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 Inc.
- external identifiers
-
- scopus:3042716135
- ISSN
- 0018-019X
- DOI
- 10.1002/hlca.19840670605
- language
- English
- LU publication?
- yes
- additional info
- Part 23 of the series ‘High-Pressure NMR Kinetics’
- id
- 1cfcbd02-e541-4bb0-8bb1-0a4d6eabb3f6
- date added to LUP
- 2017-02-06 17:59:26
- date last changed
- 2021-01-03 10:32:19
@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}}, keywords = {{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 Inc.}}, 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}}, doi = {{10.1002/hlca.19840670605}}, volume = {{67}}, year = {{1984}}, }