Organoruthenium Complexes Containing 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 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.

• Journal Article Type: Article
• Acceptance Date: Sep 12, 2023
• Online Publication Date: Sep 19, 2023
• Publication Date: 2023-09
• Deposit Date: Sep 29, 2023
• Publicly Available Date: Oct 13, 2023
• Journal: Inorganics
• Electronic ISSN: 2304-6740
• Publisher: MDPI AG
• Peer Reviewed: Peer Reviewed
• Volume: 11
• Issue: 9
• Article Number: 372
• DOI: https://doi.org/10.3390/inorganics11090372
• Keywords: Phosphinocarboxamide; metallacycle; ruthenium; P ligands; coordination chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/25391161
• Publisher URL: https://www.mdpi.com/2304-6740/11/9/372
• Additional Information: © 2023 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).