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Divergent stereoisomers of molybdenum carbonyl complexes of NHC-based pincer ligands
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Apps, Samantha L., Alflatt, Rhiannon E., Leforestier, Baptiste, Storey, Caroline M. and Chaplin, Adrian B. (2018) Divergent stereoisomers of molybdenum carbonyl complexes of NHC-based pincer ligands. Polyhedron, 143 . pp. 57-61. doi:10.1016/j.poly.2017.08.001
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Official URL: http://dx.doi.org/10.1016/j.poly.2017.08.001
Abstract
The first molybdenum complexes of widely used NHC-based CNC and C^N^C pincer ligands are described, viz. [Mo(L)(CO)3] (L = 2,6-bis(mesityl-imidazolylidene)pyridine ≡ CNC-Mes, 1; α,α’-(diimidazolylidene-dodecamethylene)lutidine ≡ C^N^C-12, 2). These complexes have been thoroughly characterised in solution and the solid-state, revealing different stereochemical preferences of the tridentate ligands depending on the nature of the scaffold. In the case of flexible C^N^C-12 an uncommon fac-coordination geometry is observed, whilst the complex of rigid CNC-Mes adopts the expected mer-configuration. For the combination of donors associated with the ligands, DFT calculations establish preferential fac-coordination, however, within the CNC (ΔΔG = +63.1 kJ·mol-1) and C^N^C (ΔΔG = +20.0 kJ·mol-1) scaffolds this conformation is significantly destabilised relative to the mer-alternative.
| Item Type: | Journal Article | ||||||||
|---|---|---|---|---|---|---|---|---|---|
| Subjects: | Q Science > QD Chemistry | ||||||||
| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||
| Library of Congress Subject Headings (LCSH): | Organometallic chemistry, Ligands, Stereoisomers, Molybdenum compounds | ||||||||
| Journal or Publication Title: | Polyhedron | ||||||||
| Publisher: | Pergamon | ||||||||
| ISSN: | 0277-5387 | ||||||||
| Official Date: | 15 March 2018 | ||||||||
| Dates: |
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| Volume: | 143 | ||||||||
| Page Range: | pp. 57-61 | ||||||||
| DOI: | 10.1016/j.poly.2017.08.001 | ||||||||
| Status: | Peer Reviewed | ||||||||
| Publication Status: | Published | ||||||||
| Access rights to Published version: | Restricted or Subscription Access | ||||||||
| Funder: | University of Warwick, European Research Council (ERC), Royal Society (Great Britain) | ||||||||
| Grant number: | 637313 (ERC) |
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