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Issue 7, 2020
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Synthesis and group 9 complexes of macrocyclic PCP and POCOP pincer ligands

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Abstract

The synthesis of macrocyclic variants of commonly employed phosphine-based pincer (pro)ligands derived from meta-xylene (PCP-14) and resorcinol (POCOP-14) is described, where the P-donors are trans-substituted with a tetradecamethylene linker. The former was accomplished using a seven-step asymmetric procedure involving (−)-cis-1-amino-2-indanol as a chiral auxiliary and ring-closing olefin metathesis. A related, but non-diastereoselective route was employed for the latter, which consequently necessitated chromatographic separation from the cis-substituted by-product. The proligands are readily metalated and homologous series of MI(CO) and MIIICl2(CO) derivatives (M = Rh, Ir) have been isolated and fully characterised in solution and the solid state. Metal hydride complexes are generated during the synthesis of the former and have been characterised in situ using NMR spectroscopy.

Graphical abstract: Synthesis and group 9 complexes of macrocyclic PCP and POCOP pincer ligands

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Supplementary files

Article information


Submitted
20 Dec 2019
Accepted
27 Jan 2020
First published
07 Feb 2020

This article is Open Access

Dalton Trans., 2020,49, 2087-2101
Article type
Paper

Synthesis and group 9 complexes of macrocyclic PCP and POCOP pincer ligands

B. Leforestier, M. R. Gyton and A. B. Chaplin, Dalton Trans., 2020, 49, 2087
DOI: 10.1039/C9DT04835A

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    [Original citation] - Published by The Royal Society of Chemistry.

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