Tailoring RuII Pyridine/Triazole Oxygenation Catalysts and Using Photoreactivity to Probe their Electronic Properties

1. tmpaのPyをトリアゾールに置き換えたリガンドを持ったRu錯体を作って、mCPBAによるシクロオクテンの水酸化反応に 使っています。

1. Fritz Weisser, 
2. Hendrik Stevens, 
3. Johannes Klein, 
4. Margarethe van der Meer, 
5. Dr. Stephan Hohloch and
6. Prof. Dr. Biprajit Sarkar^*

Author Information

1. Institute of Chemistry and Biochemistry, Freie Universität Berlin, Fabeckstrasse 34–36, 14195 Berlin (Germany)

Email: Prof. Dr. Biprajit Sarkar (biprajit.sarkar@fu-berlin.de)

^*Institute of Chemistry and Biochemistry, Freie Universität Berlin, Fabeckstrasse 34–36, 14195 Berlin (Germany)

Article first published online: 8 MAY 2015

DOI: 10.1002/chem.201406441

Abstract

Tuning of ligand properties is at the heart of influencing chemical reactivity and generating tailor-made catalysts. Herein, three series of complexes [Ru(L)(Cl)(X)]PF₆ (X=DMSO, PPh₃, or CD₃CN) with tripodal ligands (L1–L5) containing pyridine and triazole arms are presented. Triazole-for-pyridine substitution and the substituent at the triazole systematically influence the redox behavior and photoreactivity of the complexes. The mechanism of the light-driven ligand exchange of the DMSO complexes in CD₃CN could be elucidated, and two seven-coordinate intermediates were identified. Finally, tuning of the ligand framework was applied to the catalytic oxygenation of alkanes, for which the DMSO complexes were the best catalysts and the yield improved with increasing number of triazole arms. These results thus show how click-derived ligands can be tuned on demand for catalytic processes.

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