Organoruthenium Complexes Containing Hemilabile Phosphinodicarboxamide Ligands

Nolla-Saltiel, Roberto; Geer, Ana M.; Sharpe, Helen R.; Huke, Cameron D.; Taylor, Laurence J.; Linford-Wood, Thomas G.; James, Ashleigh; Allen, Jamie; Lewis, William; Blake, Alexander J.; McMaster, Jonathan; Kays, Deborah L.

Abstract

Ruthenium complexes of hemilabile phosphinocarboxamide ligands, and their use to form metallacycles using halide abstraction/deprotonation reactions are reported. Thus, [Ru(p-cym){PPh2C(=O)NHR}Cl2; R = iPr (1), Ph (2), p-tol (3)] and [Ru(p-cym){PPh2C(=O)N(R)C(=O)N(H)R}Cl2; R = Ph (4), p-tol (5)] were synthesized from [(p-cym)RuCl2]2 (p-cym = para-cymene) and phosphinocarboxamides or phosphinodicarboxamides, respectively. Single crystal X-ray diffraction measurements on 1–5 reveal coordination to ruthenium through the phosphorus donor, with an intramolecular hydrogen bond between the amine-bound proton and a metal-bound chloride. Six-membered metallacycles formed by halide abstraction/deprotonation of complexes 4 and 5 afforded [Ru(p-cym){κ2-P,N-PPh2C(=O)N(R)C(=O)NR}Cl] [R = Ph (6), p-tol (7)]. These species exist as a mixture of two rotational isomers in solution, as demonstrated by NMR spectroscopy.

Citation

Nolla-Saltiel, R., Geer, A. M., Sharpe, H. R., Huke, C. D., Taylor, L. J., Linford-Wood, T. G., James, A., Allen, J., Lewis, W., Blake, A. J., McMaster, J., & Kays, D. L. Organoruthenium Complexes Containing Hemilabile Phosphinodicarboxamide Ligands

• Working Paper Type: Working Paper
• Deposit Date: Sep 29, 2023
• Publicly Available Date: Oct 4, 2023
• Public URL: https://nottingham-repository.worktribe.com/output/23544885
• Publisher URL: https://chemrxiv.org/engage/chemrxiv/article-details/631f68ecbe03b27b1ef33624
• Additional Information: This content is a preprint and has not undergone peer review at the time of posting.