Organoruthenium Complexes Containing Phosphinodicarboxamide Ligands

• Published in: Inorganics 2023-09, Vol.11 (9), p.372
• Main Authors: 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.
• Format: Article
• Language: English
• Subjects: Amides; Chemical properties; coordination chemistry; Hydrogen bonds; Isomers; Ligands; Magnetic resonance spectroscopy; metallacycle; NMR spectroscopy; Organometallic compounds; Organoruthenium complexes; P ligands; p-Cymene; phosphinocarboxamide; Phosphorus; Rotational spectra; Ruthenium; Ruthenium compounds; Single crystals; Symmetry; X-ray diffraction
• ISSN: 2304-6740; 2304-6740
• DOI: 10.3390/inorganics11090372

Ruthenium complexes of 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.