Organoruthenium Complexes Containing Hemilabile Phosphinodicarboxamide Ligands

13 September 2022, Version 1

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.

Keywords

Phosphinocarboxamides
Phosphinodicarboxamides
Coordination Chemistry

Supplementary materials

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Description
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Supporting Information
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Contents include; general procedures, crystallographic methods, DFT Methodologies, Copies of relevant NMR spectra, DOSY NMR spectroscopic studies and Geometry optimized structures for proposed species.
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CIF data
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Crystallographic data in CIF, for all species characterized
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