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Diastereomerization Dynamics of a Bistridentate RuII Complex

Jarenmark, Martin LU ; Carlström, Göran LU ; Fredin, Lisa A. LU ; Hedberg Wallenstein, Joachim; Doverbratt, Isa LU ; Abrahamsson, Maria and Persson, Petter LU (2016) In Inorganic Chemistry 55(6). p.3015-3022
Abstract

The unsymmetrical nature of a new tridentate ligand bis(quinolinyl)-1,3-pyrazole (DQPz) is exploited in a bistridentate Ru(II) complex [Ru(DQPz)2]2+ to elucidate an unexpected dynamic diastereomerism. Structural characterization based on a combination of nuclear magnetic resonance spectroscopy and density functional theory calculations reveals the first quantifiable diastereomerization dynamics for Ru complexes with fully conjugated tridentate heteroaromatic ligands. A mechanism that involves a large-scale twisting motion of the ligands is proposed to explain the dynamic interconversion between the observed diastereomers, and the analysis of both experiments and calculations reveals a potential energy landscape... (More)

The unsymmetrical nature of a new tridentate ligand bis(quinolinyl)-1,3-pyrazole (DQPz) is exploited in a bistridentate Ru(II) complex [Ru(DQPz)2]2+ to elucidate an unexpected dynamic diastereomerism. Structural characterization based on a combination of nuclear magnetic resonance spectroscopy and density functional theory calculations reveals the first quantifiable diastereomerization dynamics for Ru complexes with fully conjugated tridentate heteroaromatic ligands. A mechanism that involves a large-scale twisting motion of the ligands is proposed to explain the dynamic interconversion between the observed diastereomers, and the analysis of both experiments and calculations reveals a potential energy landscape with a transition barrier for the diastereomerization of ∼70 kJ mol-1. The structural flexibility demonstrated around the central transition metal ion has implications for integration of complexes into catalytic and photochemical applications.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Inorganic Chemistry
volume
55
issue
6
pages
8 pages
publisher
The American Chemical Society
external identifiers
  • scopus:84961726977
  • wos:000372677800040
ISSN
0020-1669
DOI
10.1021/acs.inorgchem.5b02893
language
English
LU publication?
yes
id
51281346-356a-4652-943b-aee2c5f7e973
date added to LUP
2016-06-29 12:36:35
date last changed
2017-02-02 10:25:53
@article{51281346-356a-4652-943b-aee2c5f7e973,
  abstract     = {<p>The unsymmetrical nature of a new tridentate ligand bis(quinolinyl)-1,3-pyrazole (DQPz) is exploited in a bistridentate Ru(II) complex [Ru(DQPz)<sub>2</sub>]<sup>2+</sup> to elucidate an unexpected dynamic diastereomerism. Structural characterization based on a combination of nuclear magnetic resonance spectroscopy and density functional theory calculations reveals the first quantifiable diastereomerization dynamics for Ru complexes with fully conjugated tridentate heteroaromatic ligands. A mechanism that involves a large-scale twisting motion of the ligands is proposed to explain the dynamic interconversion between the observed diastereomers, and the analysis of both experiments and calculations reveals a potential energy landscape with a transition barrier for the diastereomerization of ∼70 kJ mol<sup>-1</sup>. The structural flexibility demonstrated around the central transition metal ion has implications for integration of complexes into catalytic and photochemical applications.</p>},
  author       = {Jarenmark, Martin and Carlström, Göran and Fredin, Lisa A. and Hedberg Wallenstein, Joachim and Doverbratt, Isa and Abrahamsson, Maria and Persson, Petter},
  issn         = {0020-1669},
  language     = {eng},
  month        = {03},
  number       = {6},
  pages        = {3015--3022},
  publisher    = {The American Chemical Society},
  series       = {Inorganic Chemistry},
  title        = {Diastereomerization Dynamics of a Bistridentate Ru<sup>II</sup> Complex},
  url          = {http://dx.doi.org/10.1021/acs.inorgchem.5b02893},
  volume       = {55},
  year         = {2016},
}