Issue 17, 2018

Group 3 metal trihalide complexes with neutral N-donor ligands – exploring their affinity towards fluoride

Abstract

Fluorination of [ScCl3(Me3-tacn)] (Me3-tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) and [ScCl3(BnMe2-tacn)] (BnMe2-tacn = 1,4-dimethyl-7-benzyl-1,4,7-triazacyclononane) by Cl/F exchange with 3 mol. equiv. of anhydrous [NMe4]F in CH3CN solution yields the corresponding [ScF3(R3-tacn)] (R3 = Me3 or BnMe2). These are the first examples of scandium fluoride complexes containing neutral co-ligands. The fluorination occurs stepwise, and using a deficit of [NMe4]F produced [ScF2Cl(Me3-tacn)]. Attempts to fluorinate [YCl3(Me3-tacn)], [YI3(Me3-tacn)], [LaCl3(Me3-tacn)(OH2)] or [MCl3(terpy)] (M = Sc, Y or La; terpy = 2,2′:6′2′′-terpyridyl) using a similar method were unsuccessful, due to the Cl/F exchange being accompanied by loss of the neutral ligand from the metal centre. Fluorination of [ScCl3(Me3-tacn)] or [ScCl3(terpy)] with Me3SnF was also successful. The products were identified as the very unusual heterobimetallic [Sc(Me3-tacn)F2(μ-F)SnMe3Cl] and [Sc(terpy)F(μ-F)2(SnMe3Cl)2], in which the Me3SnCl formed in the reaction behaves as a weak Lewis acid towards the scandium fluoride complex, linked by Sc–F–Sn bridges. [Sc(terpy)F(μ-F)2(SnMe3Cl)2] decomposes irreversibly in solution but, whilst multinuclear NMR data show that [Sc(Me3-tacn)F2(μ-F)SnMe3Cl] is dissociated into the [ScF3(Me3-tacn)] and Me3SnCl in CH3CN solution, the bimetallic complex reforms upon evaporation of the solvent. The new scandium fluoride complexes and the chloride precursors have been characterised by microanalysis, IR and multinuclear NMR (1H, 19F, 45Sc) spectroscopy as appropriate. X-ray crystal structures provide unambiguous evidence for the identities of [Sc(Me3-tacn)F2(μ-F)SnMe3Cl], [ScF2Cl(Me3-tacn)], [YI3(Me3-tacn)], [{YI2(Me3-tacn)}2(μ-O)], [ScCl3(terpy)], [YCl3(terpy)(OH2)], and [{La(terpy)(OH2)Cl2}2(μ-Cl)2]. Once formed, the [ScF3(R3-tacn)] complexes are stable in water and unaffected by a ten-fold excess of Cl or MeCO2, although they are immediately decomposed by excess F. The potential use of [ScF3(R3-tacn)] type complexes as platforms for 18F PET (positron emission tomography) radiopharmaceuticals is briefly discussed. Attempts to use the Group 3 fluoride “hydrates”, MF3·xH2O, as precursors were unsuccessful; no reaction with R3-tacn or terpy occurred either on reflux in CH3CN or under hydrothermal conditions (H2O, 180° C, 15 h). PXRD data showed that these “hydrates” actually contain the anhydrous metal trifluorides with small amounts of surface or interstitial water.

Graphical abstract: Group 3 metal trihalide complexes with neutral N-donor ligands – exploring their affinity towards fluoride

Supplementary files

Article information

Article type
Paper
Submitted
04 Feb 2018
Accepted
01 Mar 2018
First published
17 Apr 2018
This article is Open Access
Creative Commons BY license

Dalton Trans., 2018,47, 6059-6068

Group 3 metal trihalide complexes with neutral N-donor ligands – exploring their affinity towards fluoride

E. Curnock, W. Levason, M. E. Light, S. K. Luthra, G. McRobbie, F. M. Monzittu, G. Reid and R. N. Williams, Dalton Trans., 2018, 47, 6059 DOI: 10.1039/C8DT00480C

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