Dataset Information


The Lewis superacid Al[N(C6F5)2]3 and its higher homolog Ga[N(C6F5)2]3 - structural features, theoretical investigation and reactions of a metal amide with higher fluoride ion affinity than SbF5.

ABSTRACT: Herein we present the synthesis of the two Lewis acids Al[N(C6F5)2]3 (ALTA) and Ga[N(C6F5)2]3 (GATA) via salt elimination reactions. The metal complexes were characterized by NMR-spectroscopic methods and X-ray diffraction analysis revealing the stabilization of the highly Lewis acidic metal centers by secondary metal-fluorine contacts. The Lewis acidic properties of Al[N(C6F5)2]3 and Ga[N(C6F5)2]3 are demonstrated by reactions with Lewis bases resulting in the formation of metallates accompanied by crucial structural changes. The two metallates [Cs(Tol)3]+[FAl(N(C6F5)2)3]- and [AsPh4]+[ClGa(N(C6F5)2)3]- contain interesting weakly coordinating anions. The reaction of Al[N(C6F5)2]3 with trityl fluoride yielded [CPh3]+[FAl(N(C6F5)2)3]- which could find application in the activation of metallocene polymerization catalysts. The qualitative Lewis acidity of Al[N(C6F5)2]3 and Ga[N(C6F5)2]3 was investigated by means of competition experiments for chloride ions in solution. DFT calculations yielded fluoride ion affinities in the gas phase (FIA) of 555 kJ mol-1 for Al[N(C6F5)2]3 and 472 kJ mol-1 for Ga[N(C6F5)2]3. Thus, Al[N(C6F5)2]3 can be considered a Lewis superacid with a fluoride affinity higher than SbF5 (493 kJ mol-1) whereas the FIA of the corresponding gallium complex is slightly below the threshold to Lewis superacidity.


PROVIDER: S-EPMC5869307 | BioStudies | 2018-01-01T00:00:00Z

REPOSITORIES: biostudies

Similar Datasets

1000-01-01 | S-EPMC6256356 | BioStudies
1000-01-01 | S-EPMC6272166 | BioStudies
2017-01-01 | S-EPMC5540843 | BioStudies
2020-01-01 | S-EPMC7057851 | BioStudies
2019-01-01 | S-EPMC6839809 | BioStudies
2017-01-01 | S-EPMC5540842 | BioStudies
2020-01-01 | S-EPMC7317340 | BioStudies
2014-01-01 | S-EPMC4257500 | BioStudies
1000-01-01 | S-EPMC5586200 | BioStudies
2019-01-01 | S-EPMC6921613 | BioStudies