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Cu K-edge EXAFS characterisation of copper(I) arenethiolate complexes in both the solid and liquid state: detection of Cu??Cu Coordination

Cu K-edge EXAFS characterisation of copper(I) arenethiolate complexes in both the solid and liquid state: detection of Cu??Cu Coordination
Cu K-edge EXAFS characterisation of copper(I) arenethiolate complexes in both the solid and liquid state: detection of Cu??Cu Coordination
Herein we describe a structural characterisation with EXAFS of copper(I) arenethiolate complexes in both the solid and liquid state. Previously noted difficulties in the detection of the Cu??Cu interaction have been attributed to anti-phase behaviour of different Cu??Cu neighbour contributions. A data analysis procedure solely based on EXAFS parameters is presented which resolves these problems. A careful analysis of the individual coordination shells and the use of different kweightings during the data analysis are shown to be an absolute necessity to obtain reliable results. During R-space fitting, the difference file technique is used to separate, examine and compare the individual contributions. Using this technique their statistical significance and correctness can be determined. Anti-phase behaviour can be detected and accounted for in this way. An additional mixed organocopper aggregate [Cu4(SAr)2(Mes)2] with different Cu sites is analysed, which proves the value of the analysis procedure described above. Moreover, this newly developed EXAFS data analysis procedure is applicable to any other EXAFS spectrum obtained. The structural analysis of these organocopper complexes with EXAFS provides information about their actual structure and dynamic behaviour in solution. The technique can now be used to obtain insights into the reactivity of these complexes and the way in which they form catalytic reaction intermediates.
catalysts, copper, C??C coupling, exafs data analysis, exafs spectroscopy
0947-6539
5667-5678
Tromp, Moniek
48c1ebbb-579c-42b6-83bb-7188c668b322
van Bokhoven, Jeroen A.
ec7aff15-a681-4ae8-9a76-52b23a149f6b
Arink, Anne M.
a384d459-21d4-425d-a674-1670e50aeaa1
Bitter, Johannes H.
9627e7d6-8123-4a7c-854b-687818dd33fe
van Koten, Gerard
980d21db-2099-495a-bc55-548d8ec7e416
Koningsberger, Diederik C.
3e40887b-33e6-41c8-8dff-8889b4850ee8
Tromp, Moniek
48c1ebbb-579c-42b6-83bb-7188c668b322
van Bokhoven, Jeroen A.
ec7aff15-a681-4ae8-9a76-52b23a149f6b
Arink, Anne M.
a384d459-21d4-425d-a674-1670e50aeaa1
Bitter, Johannes H.
9627e7d6-8123-4a7c-854b-687818dd33fe
van Koten, Gerard
980d21db-2099-495a-bc55-548d8ec7e416
Koningsberger, Diederik C.
3e40887b-33e6-41c8-8dff-8889b4850ee8

Tromp, Moniek, van Bokhoven, Jeroen A., Arink, Anne M., Bitter, Johannes H., van Koten, Gerard and Koningsberger, Diederik C. (2002) Cu K-edge EXAFS characterisation of copper(I) arenethiolate complexes in both the solid and liquid state: detection of Cu??Cu Coordination. Chemistry - A European Journal, 8 (24), 5667-5678. (doi:10.1002/1521-3765(20021216)8:24<5667::AID-CHEM5667>3.0.CO;2-O).

Record type: Article

Abstract

Herein we describe a structural characterisation with EXAFS of copper(I) arenethiolate complexes in both the solid and liquid state. Previously noted difficulties in the detection of the Cu??Cu interaction have been attributed to anti-phase behaviour of different Cu??Cu neighbour contributions. A data analysis procedure solely based on EXAFS parameters is presented which resolves these problems. A careful analysis of the individual coordination shells and the use of different kweightings during the data analysis are shown to be an absolute necessity to obtain reliable results. During R-space fitting, the difference file technique is used to separate, examine and compare the individual contributions. Using this technique their statistical significance and correctness can be determined. Anti-phase behaviour can be detected and accounted for in this way. An additional mixed organocopper aggregate [Cu4(SAr)2(Mes)2] with different Cu sites is analysed, which proves the value of the analysis procedure described above. Moreover, this newly developed EXAFS data analysis procedure is applicable to any other EXAFS spectrum obtained. The structural analysis of these organocopper complexes with EXAFS provides information about their actual structure and dynamic behaviour in solution. The technique can now be used to obtain insights into the reactivity of these complexes and the way in which they form catalytic reaction intermediates.

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More information

Published date: 2002
Keywords: catalysts, copper, C??C coupling, exafs data analysis, exafs spectroscopy

Identifiers

Local EPrints ID: 46480
URI: http://eprints.soton.ac.uk/id/eprint/46480
ISSN: 0947-6539
PURE UUID: cca9e802-ec31-40fb-aa52-f3383cabc317

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Date deposited: 02 Jul 2007
Last modified: 08 Jan 2022 15:58

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Contributors

Author: Moniek Tromp
Author: Jeroen A. van Bokhoven
Author: Anne M. Arink
Author: Johannes H. Bitter
Author: Gerard van Koten
Author: Diederik C. Koningsberger

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