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Addition of MesN (Mes=2,4,6-Me C H ) to germylene [(NON )Ge] (NON =O(SiMe NtBu) ) (1) gives germanimine, [(NON )Ge=NMes] (2). Compound 2 behaves as a metalloid, showing reactivity reminiscent of both transition metal-imido complexes, undergoing [2+2] addition with heterocumulenes and protic sources, as well as an activated diene, undergoing a [4+2] cycloaddition, or "metallo"-Diels-Alder, reaction. In the latter case, the diene includes the Ge=N bond and π-system of the Mes substituent, which is reactive towards dienophiles including benzaldehyde, benzophenone, styrene, and phenylacetylene.
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http://dx.doi.org/10.1002/chem.201905693 | DOI Listing |
Chem Sci
July 2025
Organic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry, Faculty of Science, Utrecht University Universiteitsweg 99 3584 CG Utrecht The Netherlands
We report the synthesis, isolation, and characterisation of an N-heterocyclic germylene (NHGe) derived from a two-electron reduced Mg-synthon of the redox-active NBA ligand. This NHGe features a vacant binding pocket capable of coordinating various metals, which enables the formation of heterobimetallic Ge-Zn and Ge-Mg complexes. Electronic structure calculations reveal that the Ge-Zn interactions are weak, whilst the interactions between the metals found for the heterodinuclear Ge-Mg complex are stronger.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2023
Department of Organic Chemistry, Universidad Autónoma de Madrid, Campus de Cantoblanco C/Francisco Tomás y Valiente 7, 28049, Madrid, Spain.
Herein we report the first example of a supramolecular cage that works as a catalytic molecular reactor to perform transformations over fullerenes in aqueous medium. Taking advantage of the ability of metallo-organic Pd(II)-subphthalocyanine (SubPc) capsules to form stable host:guest complexes with C , we have prepared a water-soluble cage that provides a hydrophobic environment for conducting cycloadditions over encapsulated C , namely, Diels-Alder reactions with anthracene. Indeed, the presence of catalytic amounts of SubPc cage dissolved in water promotes co-encapsulation of insoluble C and anthracene substrates, allowing the reaction to occur inside the cavity under mild conditions.
View Article and Find Full Text PDFChemistry
February 2020
School of Chemical and Physical Sciences, Victoria University of Wellington, PO Box 600, Wellington, 6012, New Zealand.
Addition of MesN (Mes=2,4,6-Me C H ) to germylene [(NON )Ge] (NON =O(SiMe NtBu) ) (1) gives germanimine, [(NON )Ge=NMes] (2). Compound 2 behaves as a metalloid, showing reactivity reminiscent of both transition metal-imido complexes, undergoing [2+2] addition with heterocumulenes and protic sources, as well as an activated diene, undergoing a [4+2] cycloaddition, or "metallo"-Diels-Alder, reaction. In the latter case, the diene includes the Ge=N bond and π-system of the Mes substituent, which is reactive towards dienophiles including benzaldehyde, benzophenone, styrene, and phenylacetylene.
View Article and Find Full Text PDFAdv Biochem Eng Biotechnol
November 2015
School of Biological and Chemical Sciences, Queen Mary University of London, Mile End Road, London, E1 4NS, UK.
The area of biomimetic catalysis based on molecular imprinted polymers has progressed considerably over the last two decades, with research efforts focused on developing catalysts for challenging reactions and on understanding the key factors in template structure and polymer morphology that influence efficiency and selectivity. Recent advances and significant achievements in the field presented in this chapter are organized according to four topics: hydrolytic reactions of challenging substrates, oxidase mimics, metallo-enzyme mimics, and polymers that display unusual reactivity, such as in the case of reactions for which enzymes don't exist, such as Diels-Alder and Kemp elimination. For each theme, significant examples for recent literature are presented and discussed.
View Article and Find Full Text PDFChem Soc Rev
July 2014
Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, Facultat de Ciències, 17071 Girona, Spain.
The encapsulation of metal clusters in endohedral metallofullerenes (EMFs) takes place in cages that in most cases are far from being the most stable isomer in the corresponding hollow fullerenes. There exist several possible explanations for the choice of the hosting cages in EMFs, although the final reasons are actually not totally well understood. Moreover, the reactivity and regioselectivity of (endohedral metallo)fullerenes have in the past decade been shown to be generally dependent on a number of factors, such as the size of the fullerene cage, the type of cluster that is being encapsulated, and the number of electrons that are transferred formally from the cluster to the fullerene cage.
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