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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 ISSN 0277-5387.

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Official URL: http://dx.doi.org/10.1016/j.poly.2017.08.001

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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:
DateEvent
15 March 2018Published
4 August 2017Available
2 August 2017Accepted
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
Date of first compliant deposit: 15 August 2017
Date of first compliant Open Access: 4 August 2018
Funder: University of Warwick, European Research Council (ERC), Royal Society (Great Britain)
Grant number: 637313 (ERC)

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