While existing literature has primarily focused on carbene-stabilized amino- and arylborylenes of the form [(carbene)BR] (R = substituent), herein we report the generation and metallomimetic reactivity of the first carbene-stabilized alkylborylene [(CAACMe)BCy] (CAACMe = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene, Cy = cyclohexyl. Furthermore, the transition metal-like decarbonylation reactions of a borylene complex, [(CAACMe)BCy(CO)], derived from borylene [(CAACMe)BCy] and CO, are described. Additional findings described include (i) the identification of the coordination stages of the ligand to boron towards forming complexes [(CAACMe)BCyL] in the reduction route from starting material [(CAACMe)BCyBr2] and in the photolysis route from carbonyl complex [(CAACMe)BCy(CO], and (ii) insights from quantum-chemical computations regarding the molecular and electronic structure of the borylene at various stages.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.202423669 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Formation and Metallomimetic Reactivity of a Transient Dicoordinate Alkylborylene.
Angew Chem Int Ed Engl
March 2025
Julius-Maximilians-Universitat Wurzburg, Department of Chemistry, Am Hubland, 97074, Würzburg, GERMANY.
While existing literature has primarily focused on carbene-stabilized amino- and arylborylenes of the form [(carbene)BR] (R = substituent), herein we report the generation and metallomimetic reactivity of the first carbene-stabilized alkylborylene [(CAACMe)BCy] (CAACMe = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene, Cy = cyclohexyl. Furthermore, the transition metal-like decarbonylation reactions of a borylene complex, [(CAACMe)BCy(CO)], derived from borylene [(CAACMe)BCy] and CO, are described. Additional findings described include (i) the identification of the coordination stages of the ligand to boron towards forming complexes [(CAACMe)BCyL] in the reduction route from starting material [(CAACMe)BCyBr2] and in the photolysis route from carbonyl complex [(CAACMe)BCy(CO], and (ii) insights from quantum-chemical computations regarding the molecular and electronic structure of the borylene at various stages.
View Article and Find Full Text PDFDual Diborane(4) Reactivity: Lewis Acid to Bind Lewis-Basic Substrates and Electron Donor For Substrate Reduction Through Stimulated Diborane-Substrate Electron Transfer.
Chemistry
March 2025
Ruprecht-Karls-Universität Heidelberg, Institut für Anorganische Chemie, Im Neuenheimer Feld 270, 69120, Heidelberg, GERMANY.
Electron-rich ditriflato- and dibromido-diborane(4) molecules with bridging guanidinate substituents readily eliminate triflate/bromide to give monocationic diboranes displaying a dual reactivity as Lewis acids and electron donors. In this work, we report unprecedented reaction sequences in which pyrazine derivatives are first coordinated to the diborane. These coordination compounds are intensely coloured due to electronic excitations from an electron in the B-B bond to a pyrazine π* orbital.
View Article and Find Full Text PDFSubstitution and Electron Transfer in Diborane-Quinone Systems.
Chemistry
January 2025
Inorganic Chemistry, Ruprecht-Karls Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
The dual reactivity of boron compounds as Lewis acids and electron donors has spurred the development of a metallomimetic chemistry of boron compounds as a topical research theme. In this work we elaborate on the reaction of specially-designed diborane(4) compounds with quinones, as a prime example showing their dual (metallomimetic) chemistry as a Lewis acid and electron donor. The quinone is first coordinated to the diborane and then reduced by intramolecular electron transfer from the B-B bond to a quinone π* orbital.
View Article and Find Full Text PDFSynthesis and redox catalysis of Carbodiphosphorane ligated stannylene.
Nat Commun
November 2024
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, 610064, Chengdu, People's Republic of China.
Heavier group 14 carbene analogues, exhibiting transition-metal-like behavior, display remarkable capability for small molecule activation and coordination chemistry. However, their application in redox catalysis remains elusive. In this paper, we report the synthesis and isolation of a stannylene with carbodiphosphorane ligand.
View Article and Find Full Text PDFMetallomimetic C-F Activation Catalysis by Simple Phosphines.
J Am Chem Soc
January 2024
Department of Chemistry, University of York, Heslington, York YO10 5DD, U.K.
Delivering metallomimetic reactivity from simple p-block compounds is highly desirable in the search to replace expensive, scarce precious metals by cheap and abundant elements in catalysis. This contribution demonstrates that metallomimetic catalysis, involving facile redox cycling between the P(III) and P(V) oxidation states, is possible using only simple, cheap, and readily available trialkylphosphines without the need to enforce unusual geometries at phosphorus or use external oxidizing/reducing agents. Hydrodefluorination and aminodefluorination of a range of fluoroarenes was realized with good to very good yields under mild conditions.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!