Preparation and characterization of the dimeric Lewis superacid [Al(OTeF ) ] and various solvent adducts is presented. The latter range from thermally stable adducts to highly reactive, weakly bound species. DFT calculations on the ligand affinity of these Lewis acids were performed in order to rank their remaining Lewis acidity. An experimental proof of the Lewis acidity is provided by the reaction of solvent-adducts of Al(OTeF ) with [PPh ][SbF ] and OPEt , respectively. Furthermore, their reactivity towards chloride and pentafluoroorthotellurate salts as well as (CH ) SiCl and (CH ) SiF is shown. This includes the formation of the dianion [Al(OTeF ) ] .
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http://dx.doi.org/10.1002/chem.202201958 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Department of chemistry, University of California, Riverside, Riverside, CA, 92521, USA.
Sulfated zirconium oxide (SZO) catalyzes the hydrogenolysis of isotactic polypropylene (iPP, M=13.3 kDa, Đ=2.4,
J Org Chem
January 2025
Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13, 81377 Munich, Germany.
The reactions of diketene were investigated in the HF/MF and DF/MF (M = As or Sb) binary superacidic systems. Depending on the stoichiometric ratio of the Lewis acids and diketene, monoprotonated acetoacetyl fluoride and diprotonated acetoacetyl fluoride were obtained. The salts were characterized by low-temperature vibrational spectroscopy, nuclear magnetic resonance spectroscopy, and single-crystal X-ray diffraction.
View Article and Find Full Text PDFDalton Trans
December 2024
Ruprecht-Karls-Universität Heidelberg, Anorganisch-Chemisches Institut, Im Neuenheimer Feld 270, Heidelberg 69120, Germany.
Bis(catecholato)silanes were showcased as strong Lewis acids, while their inherent redox activity remained unexplored in this context. In the present work, we study the oxidation of monomeric bis(3,6-di--butyl-catecholato)silane (1), leading to the Lewis superacidic radicalic silylium ionradical 1˙+ (FIA 784 kJ mol). Oxidation of 1 with [N(-CHBr)][B(CF)] yielded [1][B(CF)], displaying strong catalytic activity in the Friedel-Crafts-dimerization, hydrodeoxygenation and carbonyl-olefin-metathesis.
View Article and Find Full Text PDFChem Sci
December 2024
Institute for Chemistry, CINSaT, University of Kassel Heinrich-Plett-Straße 40 34132 Kassel Germany https://www.uni-kassel.de/go/hybrid.
Triphospha[3]ferrocenophane Fe(CH-PTip)PCl (Tip = 2,4,6-tri(isopropyl)phenyl) has been prepared and its suitability to generate the corresponding bisphosphanylphosphenium ion has been explored. By formal addition of P to the latter, an unprecedented tetraphosphenium ion forms which likewise is capable of P transfer and qualifies as Lewis superacid based on its computed fluoride ion affinity. As a solid, this species is stable and conveniently storable, featuring a remarkably long P-P bond (2.
View Article and Find Full Text PDFChemistry
October 2024
Institut für Anorganische Chemie und Kristallographie, Universität Bremen, Leobener Straße 7, 28359, Bremen, Germany.
The C,N-chelated aryltellurenyl triflate [2-(tBuNCH)CHTe][OTf] (1) activates the Si-H bonds in the tertiary silanes RSiH via umpolung of H to H to give rise to the iminium salts (tBuN(H)CH)CHTeSiR][OTf] (2, R=Et, Ph (elusive) and R=Si(CH) isolated; OTf=OSCF) comprising Te-Si bonds, which are capable of generating silyl triflates, RSiOTf, under attack of a second equivalent of 1. The unprecedented Si-H activation was utilized in main group redox catalysis using p-quinones, which were converted into (silylated) hydroquinones.
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