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Updated: Feb 23, 2026
10:51
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
12.8K
Coordinatively Labile 18-Electron Arene Ruthenium Iminophosphonamide Complexes
Iana S Sinopalnikova1,2, Tat'yana A Peganova1, Valentin V Novikov1
1A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov str., 119991, Moscow, Russia.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|August 31, 2017
Summary
The electron-donating ability of NPN ligands and solvent polarity influence chloride dissociation from arene ruthenium complexes. This study details the thermodynamics and reactivity of these novel organometallic compounds.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Thermodynamics
Background:
- Investigates 18-electron arene ruthenium iminophosphonamide complexes with the general formula [(η⁶-arene)RuCl{(R'N)₂PR₂}] (1a-d).
- Focuses on the thermodynamics of chloride dissociation and the reactivity of related 16-electron cationic species.
Purpose of the Study:
- To assess the thermodynamics of chloride dissociation from arene ruthenium iminophosphonamides in various solvents.
- To investigate the influence of NPN ligand substituents and solvent polarity on dissociation equilibrium.
- To explore the coordination chemistry and carbonylation reactions of the resulting 16-electron cationic complexes.
Main Methods:
- Variable-temperature UV/Vis spectroscopy.
- Nuclear Magnetic Resonance (NMR) spectroscopy, including 2D EXSY ¹H NMR.
- Isolation and structural characterization of new ruthenium complexes.
Main Results:
- Chloride dissociation enthalpy (ΔH<0xE1><0xB5><0xA6>) is sensitive to the electron-donating strength of NPN substituents and solvent polarity.
- Complexes exhibit exothermic spontaneous chloride dissociation in polar solvents, influenced by ligand electronics.
- Coordination of neutral ligands (MeCN, pyridine, CO) to 16-electron complexes is reversible, dependent on ligand π-acceptor ability.
- Synthesis of rare cationic arene ruthenium carbonyl complexes (3a, 3d) and a unique carbonyl-carbamoyl complex (3c) via carbonylation.
Conclusions:
- The NPN ligand framework significantly impacts the thermodynamic stability and reactivity of arene ruthenium complexes.
- Understanding these factors enables the rational design of novel organometallic catalysts and materials.
- The study expands the known chemistry of cationic ruthenium carbonyl complexes, including unusual insertion products.
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