Publisher: Royal Society of Chemistry (RSC)

Issue: 41

License: [{"start"=>{"date-parts"=>[[2023, 9, 22]], "date-time"=>"2023-09-22T00:00:00Z", "timestamp"=>1695340800000}, "content-version"=>"am", "delay-in-days"=>629, "URL"=>"http://rsc.li/journals-terms-of-use"}]

Publication date(s): 2022/10/25 (print) 2022 (online)

Pages: 15783-15791

Volume: 51 Issue: 41

Journal: Dalton Transactions

Link: [{"URL"=>"http://pubs.rsc.org/en/content/articlepdf/2022/DT/D2DT02888C", "content-type"=>"unspecified", "content-version"=>"vor", "intended-application"=>"similarity-checking"}]

1,8-Bis(boronic ester) derivatives of naphthalene, 1,8-C10H6{B(OR)2}2, present an attractive target as receptors for the fluoride ion via B–F–B chelation, but are synthetically challenging to access due to the competing formation of a very stable anhydride containing a B–O–B motif. By contrast, unsymmetrical systems of the type 1,8-C10H6{B(OR)2}(BR′2) can be synthesized for (OR)2 = 1,2-O2C6H4 (i.e. Cat) and R′ = Mes. This system is shown to be competent for the uptake of F−, making use of a chelating mode of action and the formation of a bridging B–F–B motif between the two boron centres. However, both experimental and quantum chemical studies indicate that the μ2-F adduct is the kinetic product of fluoride uptake, with an alternative structural motif featuring a terminal B–F bond and a B–O–B bridge using one of the catechol oxygens being (marginally) more favourable thermodynamically.