Kinetic Studies of the Chirality Inversion of Salicylaldiminato-Ruthenium Using Racemic η6-p-Cymene Complexes as a Mechanistic Probe

• Published in: European journal of inorganic chemistry Vol. 2016; no. 19; pp. 3148 - 3156
• Main Authors: Komiya, Naruyoshi, Nakajima, Tomoko, Hotta, Masato, Maeda, Takatoshi, Matsuoka, Tatsuya, Kawamorita, Soichiro, Naota, Takeshi
• Format: Journal Article
• Language: English
• Published: Blackwell Publishing Ltd 01.07.2016
• Subjects: Chirality; Inversion; Kinetics; Ruthenium
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201600221

Kinetic studies of the chirality inversion of a series of mono‐ and bimetallic (p‐cymene)(salicylaldiminato)RuII complexes with halo ligands (1 and 2) in solution have been performed by means of the line‐shape method, using 1H NMR spectroscopy to evaluate the signal exchange rates between diastereotopic protons in the p‐cymene ligand. The activation parameters (ΔH‡ and ΔS‡) associated with the flipping molecular mobility were determined from variable‐temperature NMR analyses, and it was found that the neutral halo complexes 1 and 2 exhibit much lower enthalpies and entropies than the corresponding cationic pyridine analogues 3. Kinetic studies of the chirality inversion of a series of mono‐ and bimetallic (p‐cymene)(salicylaldiminato)RuII complexes with halo ligands in solution have been conducted by means of the line‐shape method, using 1H NMR spectroscopy to evaluate the signal exchange rates between diastereotopic protons in the p‐cymene ligand.