We report the synthesis of an acyclic two-coordinate germylene supported by two bulky and electron donating N-heterocyclic guanidine [IPr═N](-) ligands (IPr = [(HCNDipp)2C:]; Dipp = [2,6-(i)Pr2C6H3]), and its reactivity with molecular hydrogen to form IPr═NH, which presumably proceeds via the unstable intermediate [H2Ge(N═IPr)2]. Our attempts to isolate the corresponding silylene [:Si(N═IPr)2] led to an unexpected ligand activation/rearrangement process involving N-C(aryl) bond cleavage within the N-heterocyclic guanidine ligand; this transformation was also studied by computational methods.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ic5029838 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Site-Selective Copper(I)-Catalyzed Hydrogenation of Amides.
J Am Chem Soc
January 2025
Institut für Chemie, Technische Universität Chemnitz, Straße der Nationen 62, 09111 Chemnitz, Germany.
We present a bifunctional catalyst consisting of a copper(I)/N-heterocyclic carbene and an organocatalytic guanidine moiety that enables, for the first time, a copper(I)-catalyzed reduction of amides with H as the terminal reducing agent. The guanidine allows for reactivity tuning of the originally weakly nucleophilic copper(I) hydrides - formed in situ - to be able to react with difficult-to-reduce amides. Additionally, the guanidine moiety is key for the selective recognition of "privileged" amides based on simple and readily available heterocycles in the presence of other amides within one molecule, giving rise to hitherto unknown site-selective catalytic amide hydrogenation.
View Article and Find Full Text PDFModular Synthesis of Azines Bearing a Guanidine Core from N-Heterocyclic Carbene (NHC)-Derived Selenoureas and Diazo Reagents.
Chemistry
September 2024
Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis, 15771, Athens, Greece.
N-Heterocyclic carbene (NHC)-derived selenoureas comprise a fundamentally important class of NHC derivatives, with key applications in coordination chemistry and the determination of NHC electronic properties. Considering the broad reactivity of chalcogen-containing compounds, it is surprising to note that the use of NHC-derived selenoureas as organic synthons remains essentially unexplored. The present contribution introduces a novel, straightforward transformation leading to azines bearing a guanidine moiety, through the reaction of a wide range of NHC-derived selenoureas with commercially available diazo compounds, in the presence of triphenylphosphine.
View Article and Find Full Text PDFCatalyst- and excess reagent recycling in aza-Michael additions.
Org Biomol Chem
March 2024
University of Pannonia, Department of Organic Chemistry, Egyetem u. 10, P.O. Box 158, H-8200 Veszprém, Hungary.
16α-Azolyl-pregnenolone derivatives were prepared 2-butyl-1,1,3,3-tetramethylguanidine (-Bu-TMG) catalysed aza-Michael addition of 16-dehydropregnenolone (16-DHP) carried out in [bmim][BF]. The application of the guanidine base and the imidazolium ionic liquid made it possible to recycle not only the catalyst/solvent mixture but also the excess of the N-heterocyclic reagent. By the introduction of CO at the end of the reaction, both the guanidine base and the unreacted (excess) reagent could be converted into ionic species that remained dissolved in the ionic liquid phase, while the steroid components were extracted with an apolar solvent.
View Article and Find Full Text PDFA Guanidine-Supported π-Complex of Germanium Amenable to Intramolecular C-C Cleavage in Arene and Ge Atom Transfer.
Chemistry
November 2023
Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, Ontario L2S 3A1, Canada.
The germylone dimNHCGe (dimNHC=diimino N-heterocyclic carbene) reacts with azides N R (R=SiMe or p-tolyl) to furnish the first examples of germanium π-complexes, i. e. guanidine-ligated compounds (dimNHI-SiMe )Ge (NHI=N-heterocyclic imine, R=SiMe ) and (dimNHI-Tol)Ge (R=p-tolyl).
View Article and Find Full Text PDFMechanochemical solid state synthesis of copper(I)/NHC complexes with KPO.
Beilstein J Org Chem
April 2023
Fakultät für Naturwissenschaften, Technische Universität Chemnitz, Straße der Nationen 62, 09111 Chemnitz, Germany.
A protocol for the mechanochemical synthesis of copper(I)/N-heterocyclic carbene complexes using cheap and readily available KPO as base has been developed. This method employing a ball mill is amenable to typical simple copper(I)/NHC complexes but also to a sophisticated copper(I)/N-heterocyclic carbene complex bearing a guanidine moiety. In this way, the present approach circumvents commonly employed silver(I) complexes which are associated with significant and undesired waste formation and the excessive use of solvents.
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!