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Coordinatively Labile 18‐Electron Arene Ruthenium Iminophosphonamide Complexes
Author(s) -
Sinopalnikova Iana S.,
Peganova Tat'yana A.,
Novikov Valentin V.,
Fedyanin Ivan V.,
Filippov Oleg A.,
Belkova Natalia V.,
Shubina Elena S.,
Poli Rinaldo,
Kalsin Alexander M.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201702862
Subject(s) - chemistry , ruthenium , adduct , pyridine , dissociation (chemistry) , medicinal chemistry , ligand (biochemistry) , stereochemistry , molecule , cationic polymerization , nuclear magnetic resonance spectroscopy , solvent , enthalpy , crystallography , catalysis , organic chemistry , biochemistry , physics , receptor , quantum mechanics
The thermodynamics of chloride dissociation from the 18e arene ruthenium iminophosphonamides [(η 6 ‐arene)RuCl{(R′N) 2 PR 2 }] ( 1 a – d ) [previously known with arene=C 6 Me 6 , R=Ph, R′= p ‐Tol ( a ); R=Et, R′= p ‐Tol ( b ); R=Ph, R′=Me ( c ); and new with arene= p ‐cymene, R=Ph, R′= p ‐Tol ( d )] was assessed in both polar and apolar solvents by variable‐temperature UV/Vis, NMR, and 2D EXSY 1 H NMR methods, which highlighted the influence of the NPN ligand on the equilibrium parameters. The dissociation enthalpy Δ H d decreases with increasing electron‐donating ability of the N ‐ and P ‐substituents ( 1 a , 1 d > 1 b > 1 c ) and solvent polarity, and this results in exothermic spontaneous dissociation of 1 c in polar solvents. The coordination of neutral ligands (MeCN, pyridine, CO) to the corresponding 16e complexes [(η 6 ‐arene)Ru{(R′N) 2 PR 2 }] + PF 6 − ( 2 a – d ) is reversible; the stability of the 2⋅L adducts depends on the π‐accepting ability of L. Carbonylation of 2 a and 2 d resulted in rare examples of cationic arene ruthenium carbonyl complexes ( 3 a , 3 d ), while the monocarbonyl adduct derived from 2 c reacts further with a second equivalent of CO with conversion to carbonyl‐carbamoyl complex 3 c , in which one CO molecule is inserted into the Ru−N bond. The new complexes 1 d , 2 d , 3 a , 3 c , and 3 d were isolated and structurally characterized.