The facile preparation of weakly coordinating anions: structure and characterisation of silverpolyfluoroalkoxyaluminates AgAl(ORF)4, calculation of the alkoxide ion affinity.
Purified LiAlH4 reacts with fluorinated alcohols HORF to give LiAl(ORF)4 (RF=-CH(CF3)2, 2a; -C(CH3)(CF3)2, 2b; -C(CF3)3, 2c) in 77 to 90% yield. The crude lithium aluminates LiAl(ORF)4 react metathetically with AgF to give the silver aluminates AgAl(ORF)4 (RF=-CH(CF3)2, 3a; -C(CH3)(CF3)2, 3b; -C(CF3)3, 3c) in almost quantitative yield. The solid-state structures of solvated 3a-c showed that the silver cation is only weakly coordinated (CN(Ag)=6-10; CN = coordination number) by the solvent and/or weak cation - anion contacts Ag-X (X=O, F, Cl, C). The strength of the Ag-X contacts of 3a-c was analysed by Brown's bond-valence method and then compared with other silver salts of weakly coordinating anions (WCAs), for example [CB11H6Cl6]- and [M(OTeF5)n]- (M=B, Sb, n=4, 6). Based on this quantitative picture we showed that the Al[OC(CF3)3]4 anion is one of the most weakly coordinating anions known. Moreover, the AgAl(ORF)4 species are certainly the easiest WCAs to access preparatively (20 g in two days), additionally at low cost. The Al-O bond length of Al(ORF)4- is shortest in the sterically congested Al[OC(CF3)3]4- anion-which is stable in H2O and aqueous HNO3 (35 weight%)--and indicates a strong and highly polar Al-O bond that is resistant towards heterolytic alkoxide ion abstraction. This observation was supported by a series of HF-DFT calculations of OR-, Al(OR)3 and Al(OR)4- at the MPW1PW91 and B3LYP levels (R= CH3, CF3, C(CF3)3). The alkoxide ion affinity (AIA) is highest for R=CF3 (AlA=384 +/- 9 kJ x mol(-1)) and R= C(CF3)3 (AIA=390 +/- 3 kJ x mol(-1)), but lowest for R=CH3 (AIA=363 +/- 7 kJ X mol(-1)). The gaseous AL(ORF)4-anions are stable against the action of the strong Lewis acid ALF3(g) by 88.5 +/- 2.5 (RF=CF3) and 63 +/- 12 kJ X mol(-1) (RF=C(CF3)3), while AL(OCH3)4- decomposes with -91 +/- 2 kJ X mol(-1). Therefore the presented fluorinated aluminates AL(ORF)4- appear to be ideal candidates when large and resistant WCAs are needed, for example, in cationic homogenous catalysis, for highly electrophilic cations or for weak cationic Lewis acid/base complexes.
Krossing
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University of Karlsruhe, Germany. krossing@achpc9.chemie.uni-karlsruhe.de