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Probing the donor properties of pincer ligands using rhodium carbonyl fragments : an experimental and computational case study
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Parker, Gemma L., Lau, Samantha, Leforestier, Baptiste and Chaplin, Adrian B. (2019) Probing the donor properties of pincer ligands using rhodium carbonyl fragments : an experimental and computational case study. European Journal of Inorganic Chemistry, 2019 (33). pp. 3791-3798. doi:10.1002/ejic.201900727 ISSN 1434-1948.
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Official URL: https://doi.org/10.1002/ejic.201900727
Abstract
Metal carbonyls are commonly employed probes for quantifying the donor properties of monodentate ligands. With a view to extending this methodology to mer‐tridentate “pincer” ligands, the spectroscopic properties [ν(CO), δ13C, 1JRhC] of rhodium(I) and rhodium(III) carbonyl complexes of the form [Rh(pincer)(CO)][BArF4] and [Rh(pincer)Cl2(CO)][BArF4] have been critically analysed for four pyridyl‐based pincer ligands, with two flanking oxazoline (NNN), phosphine (PNP), or N‐heterocyclic carbene (CNC) donors. Our investigations indicate that the carbonyl bands of the rhodium(I) complexes are the most diagnostic, with frequencies discernibly decreasing in the order NNN > PNP > CNC. To gain deeper insight, a DFT‐based energy decomposition analysis was performed and identified important bonding differences associated with the conformation of the pincer backbone, which clouds straightforward interpretation of the experimental IR data. A correlation between the difference in carbonyl stretching frequencies Δν(CO) and calculated thermodynamics of the RhI/RhIII redox pairs was identified and could prove to be a useful mechanistic tool.
Item Type: | Journal Article | ||||||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||
Library of Congress Subject Headings (LCSH): | Ligands (Biochemistry) , Rhodium , Carbonyl compounds , Organometallic compounds | ||||||||||||
Journal or Publication Title: | European Journal of Inorganic Chemistry | ||||||||||||
Publisher: | Wiley-VCH Verlag GMBH | ||||||||||||
ISSN: | 1434-1948 | ||||||||||||
Official Date: | 8 September 2019 | ||||||||||||
Dates: |
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Volume: | 2019 | ||||||||||||
Number: | 33 | ||||||||||||
Page Range: | pp. 3791-3798 | ||||||||||||
DOI: | 10.1002/ejic.201900727 | ||||||||||||
Status: | Peer Reviewed | ||||||||||||
Publication Status: | Published | ||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||||||
Date of first compliant deposit: | 9 August 2019 | ||||||||||||
Date of first compliant Open Access: | 16 September 2019 | ||||||||||||
RIOXX Funder/Project Grant: |
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