Kinetic Studies of the Chirality Inversion of Salicylaldiminato-Ruthenium Using Racemic η6-p-Cymene Complexes as a Mechanistic Probe
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 diastereot...
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| Published in | European journal of inorganic chemistry Vol. 2016; no. 19; pp. 3148 - 3156 |
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| Main Authors | , , , , , , |
| Format | Journal Article |
| Language | English |
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Blackwell Publishing Ltd
01.07.2016
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| Abstract | 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. |
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| AbstractList | Kinetic studies of the chirality inversion of a series of mono‐ and bimetallic (
p
‐cymene)(salicylaldiminato)Ru
II
complexes with halo ligands (
1
and
2
) in solution have been performed by means of the line‐shape method, using
1
H NMR spectroscopy to evaluate the signal exchange rates between diastereotopic protons in the
p
‐cymene ligand. The activation parameters (Δ
H
‡
and Δ
S
‡
) 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 (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. |
| Author | Naota, Takeshi Komiya, Naruyoshi Hotta, Masato Maeda, Takatoshi Matsuoka, Tatsuya Kawamorita, Soichiro Nakajima, Tomoko |
| Author_xml | – sequence: 1 givenname: Naruyoshi surname: Komiya fullname: Komiya, Naruyoshi email: komiya@jikei.ac.jp, Department of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama, Toyonaka, Osaka 560-8531, Japan, naota@chem.es.osaka-u.ac.jp organization: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama, 560-8531, Toyonaka, Osaka, Japan – sequence: 2 givenname: Tomoko surname: Nakajima fullname: Nakajima, Tomoko organization: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama, Osaka, 560-8531, Toyonaka, Japan – sequence: 3 givenname: Masato surname: Hotta fullname: Hotta, Masato organization: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama, Osaka, 560-8531, Toyonaka, Japan – sequence: 4 givenname: Takatoshi surname: Maeda fullname: Maeda, Takatoshi organization: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama, Osaka, 560-8531, Toyonaka, Japan – sequence: 5 givenname: Tatsuya surname: Matsuoka fullname: Matsuoka, Tatsuya organization: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama, Osaka, 560-8531, Toyonaka, Japan – sequence: 6 givenname: Soichiro surname: Kawamorita fullname: Kawamorita, Soichiro organization: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama, Osaka, 560-8531, Toyonaka, Japan – sequence: 7 givenname: Takeshi surname: Naota fullname: Naota, Takeshi email: naota@chem.es.osaka-u.ac.jp, Department of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama, Toyonaka, Osaka 560-8531, Japan, naota@chem.es.osaka-u.ac.jp organization: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Machikaneyama, Osaka, 560-8531, Toyonaka, Japan |
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| Snippet | 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... Kinetic studies of the chirality inversion of a series of mono‐ and bimetallic ( p ‐cymene)(salicylaldiminato)Ru II complexes with halo ligands ( 1 and 2 ) in... |
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| StartPage | 3148 |
| SubjectTerms | Chirality Inversion Kinetics Ruthenium |
| Title | Kinetic Studies of the Chirality Inversion of Salicylaldiminato-Ruthenium Using Racemic η6-p-Cymene Complexes as a Mechanistic Probe |
| URI | https://api.istex.fr/ark:/67375/WNG-4QMX8T9B-6/fulltext.pdf https://onlinelibrary.wiley.com/doi/abs/10.1002%2Fejic.201600221 |
| Volume | 2016 |
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