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Synthesis and rhodium complexes of macrocyclic PNP and PONOP pincer ligands
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Hood, Thomas M., Gyton, Matthew R. and Chaplin, Adrian B. (2020) Synthesis and rhodium complexes of macrocyclic PNP and PONOP pincer ligands. Dalton Transactions, 49 (7). pp. 2077-2086. doi:10.1039/C9DT04474D ISSN 1477-9226.
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Official URL: https://doi.org/10.1039/C9DT04474D
Abstract
The synthesis of macrocyclic variants of commonly employed phosphine-based pincer ligands derived from lutidine (PNP-14) and 2,6-dihydroxypyridine (PONOP-14) is described, where the P-donors are trans-substituted with a tetradecamethylene linker. This was accomplished using an eight-step procedure involving borane protection, ring-closing olefin metathesis, chromatographic separation from the cis-substituted diastereomers, and borane deprotection. The rhodium coordination chemistry of these ligands has been explored, aided by the facile synthesis of 2,2′-biphenyl (biph) adducts [Rh(PNP-14)(biph)][BArF4] and [Rh(PONOP-14)(biph)][BArF4] (ArF = 3,5-(CF3)2C6H3). Subsequent hydrogenolysis enabled generation of dihydrogen, ethylene and carbonyl derivatives; notably the ν(CO) bands of the carbonyl complexes provide a means to compare the donor properties of the new pincer ligands with established acyclic congeners.
| Item Type: | Journal Article | |||||||||||||||
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| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | |||||||||||||||
| Journal or Publication Title: | Dalton Transactions | |||||||||||||||
| Publisher: | Royal Society of Chemistry | |||||||||||||||
| ISSN: | 1477-9226 | |||||||||||||||
| Official Date: | 8 January 2020 | |||||||||||||||
| Dates: |
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| Volume: | 49 | |||||||||||||||
| Number: | 7 | |||||||||||||||
| Page Range: | pp. 2077-2086 | |||||||||||||||
| DOI: | 10.1039/C9DT04474D | |||||||||||||||
| Status: | Peer Reviewed | |||||||||||||||
| Publication Status: | Published | |||||||||||||||
| Access rights to Published version: | Open Access (Creative Commons) | |||||||||||||||
| Date of first compliant deposit: | 20 December 2019 | |||||||||||||||
| Date of first compliant Open Access: | 27 March 2020 | |||||||||||||||
| RIOXX Funder/Project Grant: |
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