Lewis acids are highly sought after for their applications in sensing, small-molecule activation, and catalysis. When combined with π-conjugated molecular frameworks, Lewis acids with unique optoelectronic properties can be realized. Here, we use a tridentate formazanate ligand to create a planar, redox-active, fluorescent, and strongly Lewis-acidic borenium cation. We also demonstrate that this compound can act as a colourimetric probe for reactivity.
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http://dx.doi.org/10.1039/d1cc03873g | DOI Listing |
J Org Chem
January 2025
Department of Organic Chemistry and Biochemistry, Rud̵er Bošković Institute, Bijenička Cesta 54, Zagreb 10 000, Croatia.
BODIPY photocages (photocleavable protective groups) have stirred interest because they can release biologically active cargo upon visible light excitation. We conducted combined theoretical and experimental investigations on selected BODIPY photocages to elucidate the mechanism of the competing photocleavage at the boron and -position. Based on the computations, the former reaction involves elongation of the B-C bond, yielding a tight borenium cation and methyl anion.
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December 2024
Department of Inorganic Chemistry, Faculty of Chemistry and Advanced Materials Center, Gdańsk University of Technology, Narutowicza 11/12, 80-233 Gdańsk, Poland.
The reactivity of the phosphinoborenium cation supported by a 1,3,4,5-tetramethylimidazolin-2-ylidene ligand toward small molecules was explored. The phosphinoborenium cation exhibited dual Lewis acid-base properties due to the presence of the Lewis acidic boron center and the Lewis basic phosphido ligand connected by a covalent bond. The reaction of the title cation with CO led to the insertion of a CO molecule into the P-B bond.
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January 2025
Department of Chemical Sciences, Indian Institute of Science Education and Research Mohali, Knowledge City, Sector 81, SAS Nagar, Mohali, Punjab, 140306, India.
Hydride abstraction from the borane adduct, (BICAAC) ⋅ BH afforded the hydride bridged dinuclear borenium ion equivalent complexes 1 and 2 that have been characterized by various spectroscopic and spectrometric techniques followed by the assessment of Lewis acidity using the Gutmann-Beckett method. The single crystal X-ray structure of complex 2 revealed the presence of discrete ions in the solid state. The complex (BICAAC) ⋅ BH(OTf) (3), obtained from the reaction of (BICAAC) ⋅ BH with MeOTf, formed the corresponding boronium cations [(BICAAC) ⋅ BH(L)](OTf) on reaction with Lewis bases (L= pyridine (4) and DMAP (5)).
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December 2024
Institute of Inorganic Chemistry of Czech Academy of Sciences, Husinec-Řež 1001, 250 68, Czech Republic, Řež.
Herein, we present the preparation of a series of electronically and/or sterically distinct borenium-type species based on a simple 2-arylpyridine scaffold. Corresponding arylpyridine was firstly subjected to electrophilic borylation (BBr/i-PrNEt) and formed BBr chelate was reduced with LiAlH to yield arylpyridine boron dihydride. Elimination of one hydride led to Lewis acidic borenium-like products.
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August 2024
Department of Chemistry, Indian Institute of Technology Indore, Madhya Pradesh, 453552, India.
A series of boron difluoro bis(diiminate) complexes have been prepared and used to obtain triflate substituted fluoroborane complexes. The corresponding well-defined bis(borenium) cations were subsequently synthesized and structurally authenticated. We are also presenting the first experimental and theoretical study of bis(borenium) cations that are derivative of cationic borinic acid.
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