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Deactivation of a ruthenium(II) N-heterocyclic carbene p-cymene complex during transfer hydrogenation catalysis

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Abstract

A ruthenium (II) N-heterocyclic carbene (NHC) complex was synthesized to investigate ligand dissociation as a possible deactivation pathway for the catalytic cycle of a transfer hydrogenation reaction. Diiodo(1,3-dimethylbenzimidazole-2-ylidene)(p-cymene)ruthenium(II) was synthesized for use as the catalytic species and characterized using physico-chemical, spectroscopic methods, and single crystal X-ray diffraction. The transfer of hydrogen from isopropanol to acetophenone was followed using 1H NMR. We observed 94% conversion of the substrate to the alcohol product after 1 h. We also found that the p-cymene complex decomposed during the catalytic reaction to the extent of 80% deactivation after 1 h, based on 1H NMR spectrometry. From Gaussian calculations, an ultraviolet–visible spectrum that is in excellent agreement with the actual spectrum was computed, giving insight into the nature of the absorptions observed experimentally.

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Acknowledgements

JRM would like to thank Fairfield University for awarding him a generous sabbatical leave when part of this research was accomplished. JRM thanks Professor Robert Crabtree for hosting him during his sabbatical leave and for helpful suggestions. This work was supported by generous funding from the Fairfield University Summer Research Kuck Fund (NAB, SCB, and RMK). The authors (NAB, CAVA, SCB, MEM, and RMK) acknowledge support from Fairfield University Hardiman and Lawrence Scholarships for undergraduate research expenses. MAL is grateful for receipt of an NTID Faculty Evaluation and Development (FEAD) grant. We all thank the reviewers for helpful suggestions as we revised the manuscript.

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Author notes

  1. Nicholas A. Bernier

    Present address: Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA, 90095, USA

  2. Christopher A. Van Akin

    Present address: University of Connecticut School of Medicine, 263 Farmington Avenue, Farmington, CT, 06030, USA

  3. Sheila C. Bonitatibus

    Present address: Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, MA, 02215, USA

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Fairfield University, 1073 North Benson Road, Fairfield, CT, 06824, USA

    John R. Miecznikowski, Nicholas A. Bernier, Christopher A. Van Akin, Sheila C. Bonitatibus, Maura E. Morgan & Rami M. Kharbouch

  2. Department of Chemistry, Yale University, 225 Prospect Street, New Haven, CT, 06520-8107, USA

    Brandon Q. Mercado

  3. Department of Science and Mathematics, National Technical Institute for the Deaf, Rochester Institute of Technology, 52 Lomb Memorial Drive, Rochester, NY, 14623, USA

    Matthew A. Lynn

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Miecznikowski, J.R., Bernier, N.A., Van Akin, C.A. et al. Deactivation of a ruthenium(II) N-heterocyclic carbene p-cymene complex during transfer hydrogenation catalysis. Transit Met Chem 43, 21–29 (2018). https://doi.org/10.1007/s11243-017-0189-x

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