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Updated: Dec 31, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Synthesis and rhodium complexes of macrocyclic PNP and PONOP pincer ligands
Thomas M Hood1, Matthew R Gyton, Adrian B Chaplin
1Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, UK. a.b.chaplin@warwick.ac.uk.
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.
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