Interplay between oxidative addition and reductive elimination at a diruthenium complex bearing the bis(diphenylphosphanyl)amine ligand
-
Tobias Mayer
Abstract
The compound described in a previous report [Ru2(CO)4(µ-H)(µ-PtBu2)(µ-dppa)] [dppa = bis(diphenylphosphanyl)amine, 1] crystallizes from acetone/ethanol as a solvate stabilized in the solid by an intermolecular hydrogen bonding between the NH function of the dppa ligand and an ethanol molecule (Mayer, T.; Böttcher, H.-C. Polyhedron 2013, 50, 507−511). Surprisingly, by the use of n-pentane as the antisolvent during crystal growth for X-ray diffraction purposes an isomer of compound 1 was obtained. A deprotonation of the NH function within the dppa ligand in 1 occurred accompanied by an intramolecular oxidative addition of the proton towards the diruthenium core resulting in the novel compound [Ru2(CO)4(µ-H)2(µ-PtBu2)(µ-dppa−H)] (2), [(dppa−H) = [dppa−H+]− = Ph2PNPPh2 −, bis(diphenylphosphanyl)amide]. By dissolution of solid 2 in polar solvents a transformation back to 1 (reductive elimination) occurred as clearly indicated in solution by the NMR data for complex 1. Therefore, compound 2 has been characterized only in the solid state by elemental analysis, IR spectroscopy, mass spectrometry and single-crystal X-ray diffraction.
Funding source: Department of Chemistry of the Ludwig-Maximilians-Universität Munich
-
Research ethics: Not applicable.
-
Informed consent: Not applicable.
-
Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved its submission.
-
Use of Large Language Models, AI and Machine Learning Tools: None declared.
-
Conflict of interest: The authors state no conflict of interest.
-
Research funding: This work was supported by the Department of Chemistry of the Ludwig-Maximilians-Universität Munich.
-
Data availability: The data that support the findings of this study are available from the corresponding author upon reasonable request.
References
1. Mayer, T.; Böttcher, H.-C. Polyhedron 2013, 50, 507–511.10.1016/j.poly.2012.11.049Search in Google Scholar
2. Mayer, T.; Mayer, P.; Böttcher, H.-C. J. Organomet. Chem. 2014, 751, 368–373.10.1016/j.jorganchem.2013.08.017Search in Google Scholar
3. Mayer, T.; Böttcher, H.-C. Polyhedron 2014, 69, 240–243.10.1016/j.poly.2013.12.009Search in Google Scholar
4. Böttcher, H.-C.; Graf, M.; Mereiter, K.; Kirchner, K. Organometallics 2004, 23, 1269–1273; https://doi.org/10.1021/om030618s.Search in Google Scholar
5. Mayer, T.; Mayer, P.; Böttcher, H.-C. J. Organomet. Chem. 2012, 700, 41–47.10.1016/j.jorganchem.2011.11.012Search in Google Scholar
6. Witt, M.; Roesky, H. W. Chem. Rev. 1994, 94, 1163–1181; https://doi.org/10.1021/cr00029a001.Search in Google Scholar
7. Bhattacharyya, P.; Wollins, J. D. Polyhedron 1995, 14, 3367–3388.10.1016/0277-5387(95)00103-YSearch in Google Scholar
8. Fliedel, C.; Ghisolfi, A.; Braunstein, P. Chem. Rev. 2016, 116, 9237–9304 and references cited therein https://doi.org/10.1021/acs.chemrev.6b00153.Search in Google Scholar PubMed
9. Eusamio, J.; Grabulosa, A. Dalton Trans. 2025, 54, 5969–6004 and references cited therein https://doi.org/10.1039/d4dt03572k.Search in Google Scholar PubMed
10. Böttcher, H.-C.; Heinemann, J. Z. Anorg. Allg. Chem. 2020, 646, 1787–1789.10.1002/zaac.202000359Search in Google Scholar
11. Pohl, D.; Ellermann, J.; Knoch, F. A.; Moll, M.; Bauer, W. Chem. Ber. 1994, 127, 2167–2171; https://doi.org/10.1002/cber.1491271112.Search in Google Scholar
12. Pohl, D.; Ellermann, J.; Knoch, F. A.; Moll, M.; Bauer, W. J. Organomet. Chem. 1994, 481, 259–274; https://doi.org/10.1016/0022-328x(94)85035-6.Search in Google Scholar
13. Ellermann, J.; Utz, J.; Knoch, F. A.; Moll, M. Z. Anorg. Allg. Chem. 1996, 622, 1871–1878; https://doi.org/10.1002/zaac.19966221111.Search in Google Scholar
14. CrysAlisPro (Version 1.171.33.41; Release 06-05-2009 CrysAlis171.NET); Oxford Diffraction Ltd.: Abingdon, Oxford (U. K.), 2009.Search in Google Scholar
15. Sheldrick, G. M. Acta Crystallogr. 2015, C71, 3–8.Search in Google Scholar
16. Farrugia, L. J. J. Appl. Crystallogr. 2012, 45, 849–854; https://doi.org/10.1107/s0021889812029111.Search in Google Scholar
© 2025 Walter de Gruyter GmbH, Berlin/Boston
Articles in the same Issue
- Frontmatter
- In this issue
- Research Articles
- Chemical aspects of the preparation of Vulcanised Fibre using zinc chloride hydrates: from a brief history to a new consideration of the key reactions in ionic liquids
- On the preparation and spectral properties of some hydroxy-substituted triphenylmethane dyes
- High-pressure synthesis and crystal structure of Ga5Na1–x B12O26–x (OH) x (x = 0.12)
- Intermetallic phases with Ho4Ir13Ge9-type structure
- Interplay between oxidative addition and reductive elimination at a diruthenium complex bearing the bis(diphenylphosphanyl)amine ligand
- Anthracene-d- and l-phenylalanine derivatives: synthesis, dual-state emission, mechanochromic luminescence, chiroptical property and enantioselective recognition of free amino acids
- Synthesis, structures and optical properties of 3,3′-disubstituted biphenyl compounds
Articles in the same Issue
- Frontmatter
- In this issue
- Research Articles
- Chemical aspects of the preparation of Vulcanised Fibre using zinc chloride hydrates: from a brief history to a new consideration of the key reactions in ionic liquids
- On the preparation and spectral properties of some hydroxy-substituted triphenylmethane dyes
- High-pressure synthesis and crystal structure of Ga5Na1–x B12O26–x (OH) x (x = 0.12)
- Intermetallic phases with Ho4Ir13Ge9-type structure
- Interplay between oxidative addition and reductive elimination at a diruthenium complex bearing the bis(diphenylphosphanyl)amine ligand
- Anthracene-d- and l-phenylalanine derivatives: synthesis, dual-state emission, mechanochromic luminescence, chiroptical property and enantioselective recognition of free amino acids
- Synthesis, structures and optical properties of 3,3′-disubstituted biphenyl compounds
