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Article Abstract
Computational investigations were carried out to probe the potential of several dicoordinate, singly base-stabilized borylenes of the form [L→BR] (L=neutral Lewis base) in dinitrogen binding. The calculated reaction free energies and activation barriers associated with the formation of mono- and diborylene-N adducts suggest the presence of thermally surmountable kinetic barriers towards their possible isolation. Our results show that the exergonicity of dinitrogen activation and fixation is linearly dependent on the natural charge at the boron center, which can be tuned to design novel boron-based compounds with potential applications to small-molecule activation. EDA-NOCV analysis reveals strong binding of dinitrogen to these base-stabilized borylenes.
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| http://dx.doi.org/10.1002/chem.202104123 | DOI Listing |
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View Article and Find Full Text PDFRhodium-mediated Assembly of New Heterocycles: From Borylenes to Oxaboroles.
Angew Chem Int Ed Engl
March 2025
Department of Chemistry and Biochemistry, University of Lethbridge, 4401 University Dr. W., Lethbridge, AB, Canada.
Base-stabilized rhodium borylene complex κ-L(CO)Rh(BMes), 2; κ-L=κ-NN'-Rh,κ-N-B-(2,5-[PrP=N(4-PrCH)]-N'(CH)); Mes=mesityl, reacts with a series of alkynes (PhC≡C-R; R=Ph, Me, COEt, H) to yield unique structures whereby the alkyne has regioselectively added across boron and the carbon atom of a CO ligand. The resulting complexes, LRh[C(O)C(Ph)C(R)B(Mes)], 3, react with additional CO to afford cycle-containing products, L(CO)Rh ), 5, that ultimately release highly functionalized organic heterocycles of the form =NPipp (Pipp=4-PrCH), 6. These oxaboroles, which were assembled from a primary hydroborane, CO, an alkyne, and an azide-generated NPipp, are structurally analogous to two of the five boron-containing therapeutics approved by the FDA.
View Article and Find Full Text PDFBinding of base-stabilized borylenes with transition metals and formation of metal only Lewis pairs.
Dalton Trans
January 2025
Department of Chemical Sciences, Tezpur University, Napaam 784028, Assam, India.
Article Synopsis
- Computational studies using Density Functional Theory suggest that stable borylenes, which are mono Lewis base-stabilized, can effectively bind to transition metal complexes like iron (Fe) and nickel (Ni).* -
- This binding enhances the Lewis basicity of the metal centers, leading to the creation of distinct metal-only Lewis pairs (MOLPs) involving complexes like [L(CO)Fe → GaCl] and [L(CO)Ni → GaCl], where L represents electron donating ligands.* -
- The research further explores the interactions between different ligands and the metals, utilizing advanced analytical methods such as QTAIM and EDA-NOCV.*
Experimental and Computational Study of a Confirmed Borylene-to-Diborene Dimerization.
J Am Chem Soc
October 2023
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
While the dimerization of heavier group 13 carbene analogues to the corresponding alkene analogues is known and relatively well understood, the dimerization of dicoordinate borylenes (LRB:, L = neutral donor; R = anionic substituent) to the corresponding diborenes (LRB═BRL) has never been directly observed. In this study we present the first example of a formal borylene-to-diborene dimerization through abstraction of a labile phosphine ligand from the tricoordinate hydroborylene precursor (CAAC)(MeP)BH (CAAC = cyclic alkyl(amino)carbene) by bulky Lewis-acidic dihaloboranes (BXY, X = Cl, Br, Y = aryl, boryl), generating the corresponding dihydrodiborene (CAAC)HB═BH(CAAC) and (MeP)BXY as the byproduct. An in-depth experimental and computational mechanistic analysis shows that this seemingly simple process (2 LL'BH + 2 BXY → LHB═BHL + 2 L'BXY) is in fact based on a complex sequence of finely tuned processes, involving the one-electron oxidation of and PMe abstraction from the borylene precursor by BXY, multiple halide transfers between (di)boron intermediates and BXY/[BXY], and multiple one-electron redox processes between diboron intermediates and the borylene precursor, which make the reaction ultimately autocatalytic in [(CAAC)(MeP)BH].
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Inorg Chem
June 2023
Department of Chemical Sciences, Tezpur University, Napaam 784028, Assam, India.
Computational investigations were carried out using density functional theory (ωB97XD(toluene)/6-311+G*) on a series of base-stabilized borylenes to understand their ligand properties and potential toward the activation of enthalpically strong E-H bonds (E = H, NH, SiHPh, and CH) as well as binding with small molecules such as CO and CNMe. The calculated reaction free energies and activation barriers suggest the ability of hitherto unexplored carbene-stabilized borylenes to not only split such bonds but also bind with CO and CNMe. A detailed mechanistic study of these bond activation processes reveals the noninnocent behavior of the carbene moiety attached to the boron center, thereby leading to cooperative splitting of the bonds of interest.
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