Template synthesis and theoretical investigation of [CuII 2CuI3K6(μ6-Cl)(μ 3-OtBu)12]: The first mixed-valence copper alkoxide

Angewandte Chemie - International Edition

Volumn 42, Issue 34, 2003, Pages 4036-4039

  Ahlrichs, Reinhart ^a   Anson, Christopher E ^a   Fenske, Dieter ^a   Hampe, Oliver ^b   Rothenberger, Alexander ^a   Sierka, Marek ^a  

^a UNIVERSITY OF KARLSRUHE   (Germany)

^b KARLSRUHE INSTITUTE OF TECHNOLOGY   (Germany)

Author keywords

Copper; Density functional calculations; Mixed valence compounds; Template synthesis; X ray diffraction

Indexed keywords

COMPLEXATION; COPPER COMPOUNDS; REACTION KINETICS; SYNTHESIS (CHEMICAL);

DISPROPORTIONATION REACTIONS;

ORGANIC COMPOUNDS;

CHLORIDE; COPPER CHLORIDE; COPPER DERIVATIVE; POTASSIUM DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; PRECIPITATION; ROOM TEMPERATURE; SYNTHESIS; THEORY;

EID: 0141762382     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200351395     Document Type: Article

References (28)

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13. All calculations were performed with the TURBOMOLE program package. a) R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165-169; b) O. Treutler, R. Ahlichs, J. Chem. Phys. 1995, 102, 346-354. We used the Becke-Perdew (BP86) exchange-correlation functional within the resolution of the identity (RI) approximation; c) A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100; d) S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211; e) J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; erratum: J. P. Perdew, Phys. Rev. B 1986, 34, 7406; f) K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 242, 652. The basis and auxiliary basis set used in the DFT calculations was triple-valence basis and auxiliary basis sets with one polarization function (TZVP); g) A. Schäfer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571-2577; h) A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835; i) K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119-124.
14. All calculations were performed with the TURBOMOLE program package. a) R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165-169; b) O. Treutler, R. Ahlichs, J. Chem. Phys. 1995, 102, 346-354. We used the Becke-Perdew (BP86) exchange-correlation functional within the resolution of the identity (RI) approximation; c) A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100; d) S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211; e) J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; erratum: J. P. Perdew, Phys. Rev. B 1986, 34, 7406; f) K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 242, 652. The basis and auxiliary basis set used in the DFT calculations was triple-valence basis and auxiliary basis sets with one polarization function (TZVP); g) A. Schäfer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571-2577; h) A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835; i) K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119-124.
15. All calculations were performed with the TURBOMOLE program package. a) R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165-169; b) O. Treutler, R. Ahlichs, J. Chem. Phys. 1995, 102, 346-354. We used the Becke-Perdew (BP86) exchange-correlation functional within the resolution of the identity (RI) approximation; c) A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100; d) S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211; e) J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; erratum: J. P. Perdew, Phys. Rev. B 1986, 34, 7406; f) K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 242, 652. The basis and auxiliary basis set used in the DFT calculations was triple-valence basis and auxiliary basis sets with one polarization function (TZVP); g) A. Schäfer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571-2577; h) A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835; i) K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119-124.
16. All calculations were performed with the TURBOMOLE program package. a) R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165-169; b) O. Treutler, R. Ahlichs, J. Chem. Phys. 1995, 102, 346-354. We used the Becke-Perdew (BP86) exchange-correlation functional within the resolution of the identity (RI) approximation; c) A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100; d) S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211; e) J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; erratum: J. P. Perdew, Phys. Rev. B 1986, 34, 7406; f) K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 242, 652. The basis and auxiliary basis set used in the DFT calculations was triple-valence basis and auxiliary basis sets with one polarization function (TZVP); g) A. Schäfer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571-2577; h) A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835; i) K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119-124.
17. All calculations were performed with the TURBOMOLE program package. a) R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165-169; b) O. Treutler, R. Ahlichs, J. Chem. Phys. 1995, 102, 346-354. We used the Becke-Perdew (BP86) exchange-correlation functional within the resolution of the identity (RI) approximation; c) A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100; d) S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211; e) J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; erratum: J. P. Perdew, Phys. Rev. B 1986, 34, 7406; f) K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 242, 652. The basis and auxiliary basis set used in the DFT calculations was triple-valence basis and auxiliary basis sets with one polarization function (TZVP); g) A. Schäfer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571-2577; h) A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835; i) K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119-124.
18. All calculations were performed with the TURBOMOLE program package. a) R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165-169; b) O. Treutler, R. Ahlichs, J. Chem. Phys. 1995, 102, 346-354. We used the Becke-Perdew (BP86) exchange-correlation functional within the resolution of the identity (RI) approximation; c) A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100; d) S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211; e) J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; erratum: J. P. Perdew, Phys. Rev. B 1986, 34, 7406; f) K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 242, 652. The basis and auxiliary basis set used in the DFT calculations was triple-valence basis and auxiliary basis sets with one polarization function (TZVP); g) A. Schäfer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571-2577; h) A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835; i) K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119-124.
19. All calculations were performed with the TURBOMOLE program package. a) R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165-169; b) O. Treutler, R. Ahlichs, J. Chem. Phys. 1995, 102, 346-354. We used the Becke-Perdew (BP86) exchange-correlation functional within the resolution of the identity (RI) approximation; c) A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100; d) S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211; e) J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; erratum: J. P. Perdew, Phys. Rev. B 1986, 34, 7406; f) K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 242, 652. The basis and auxiliary basis set used in the DFT calculations was triple-valence basis and auxiliary basis sets with one polarization function (TZVP); g) A. Schäfer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571-2577; h) A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835; i) K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119-124.
20. All calculations were performed with the TURBOMOLE program package. a) R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165-169; b) O. Treutler, R. Ahlichs, J. Chem. Phys. 1995, 102, 346-354. We used the Becke-Perdew (BP86) exchange-correlation functional within the resolution of the identity (RI) approximation; c) A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100; d) S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211; e) J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; erratum: J. P. Perdew, Phys. Rev. B 1986, 34, 7406; f) K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 242, 652. The basis and auxiliary basis set used in the DFT calculations was triple-valence basis and auxiliary basis sets with one polarization function (TZVP); g) A. Schäfer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571-2577; h) A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835; i) K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119-124.
21. All calculations were performed with the TURBOMOLE program package. a) R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165-169; b) O. Treutler, R. Ahlichs, J. Chem. Phys. 1995, 102, 346-354. We used the Becke-Perdew (BP86) exchange-correlation functional within the resolution of the identity (RI) approximation; c) A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100; d) S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200-1211; e) J. P. Perdew, Phys. Rev. B 1986, 33, 8822-8824; erratum: J. P. Perdew, Phys. Rev. B 1986, 34, 7406; f) K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 242, 652. The basis and auxiliary basis set used in the DFT calculations was triple-valence basis and auxiliary basis sets with one polarization function (TZVP); g) A. Schäfer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571-2577; h) A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835; i) K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119-124.
22. 3v symmetry. Differences of Cu-O bond distances are less than 0.01 Å and of O-Cu-O bond angles less than 2°.
23. The MP2 calculations with frozen-core approximation were carried out using the RI-MP2 method and TZVPP basis and auxiliary basis sets on all atoms. a) F. Weigend, M. Häser, Theor. Chem. Acc. 1997, 97, 331-340; b) F. Weigend, Phys. Chem. Chem. Phys, 2002, 4, 4285-4291.
24. The MP2 calculations with frozen-core approximation were carried out using the RI-MP2 method and TZVPP basis and auxiliary basis sets on all atoms. a) F. Weigend, M. Häser, Theor. Chem. Acc. 1997, 97, 331-340; b) F. Weigend, Phys. Chem. Chem. Phys, 2002, 4, 4285-4291.
25. 3] units in A.
26. II-O bond angles from 109° to 117°.
27. I center. Consideration of intermolecular steric interactions between tBu groups indicated that the disorder of these nine ligands was correlated, two other ligands showed 50:50 disorder. CCDC-205464 (1a) and CCDC-205465 (1b) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uldconts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam.ac.uk).
28. G. M. Sheldrick, SHELXTL-97, University of Göttingen, Göttingen (Germany), 1997.