The possibility of using aza-dipyrromethene (a-DPM) ligands to stabilize compounds containing low-valent main group elements is demonstrated through the isolation of germylenes, a-DPM(p-tol)GeCl (2), a-DPM(Naph)GeCl (6), and a-DPM(Naph)GeN(TMS) (7) (tol=tolyl, Naph=naphthyl). Because of the presence of the a-DPM ligand, these germylenes exhibit an absorption maximum at around 640 nm, a highly red-shifted value previously unknown for germylenes.
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http://dx.doi.org/10.1002/asia.202300365 | DOI Listing |
Nat Chem
January 2025
Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr, Germany.
The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis and characterization of a highly reduced bismuth salt featuring a cationic core based on three contiguous Bi(I) centres. The triatomic bismuth-based core exhibits an electronic configuration that mimics the canonical description of the archetypical carbon-based π-allyl cation.
View Article and Find Full Text PDFMolecules
November 2024
School of Environmental and Chemical Engineering, Zhaoqing University, Zhaoqing 526061, China.
Non-noble metals catalyzed carbonylative reactions serve as straightforward and sustainable methods for the synthesis of functionalized carbonyl-containing compounds. Herein, a low-valent-tungsten-catalyzed reaction that enables the coupling of aryl iodides and alcohols or phenols was disclosed, employing the readily available W(CO) as the effective catalyst and PPh as ligand. Under the optimal reaction conditions, aryl iodides smoothly underwent carbonylative coupling reactions with alcohols or phenols, processing the feature of broad substrate scope and good functional groups tolerance.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of Chemistry and Research Center for Chemical Biology and Omics Analysis, College of Science, Southern University of Science and Technology, Shenzhen, 518055, China.
A 1,4,2-diazasilole containing a low-valent silicon atom has been synthesized employing a bulky imino N-heterocyclic carbene ligand. This molecular structure is characterized by a mesoionic CNSi five-membered ring, notable for its delocalized π electrons, intrinsic charge-separated zwitterionic properties, and a distinctly nucleophilic silicon center, culminating in 6π aromaticity. This compound manifests either mesoionic silylene or silylone characteristics upon coordination with transition metals.
View Article and Find Full Text PDFChem Asian J
January 2025
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi, 110016, India.
Catalysis using low-valent main-group compounds is usually done under inert conditions; no example of such catalysis has been doable entirely in ambient conditions until now. This aspect is addressed in this work through an air- and water-stable germylene cation [DPMGe][(OH)B(CF)] (2) (DPM=dipyrromethene); it efficiently catalyzes aldehyde and ketone hydrosilylations under ambient conditions. Detailed theoretical studies reveal that compound 2's stability is bolstered by the interaction between the anion and germanium's frontier orbitals.
View Article and Find Full Text PDFChemistry
January 2025
School of Molecular Sciences, The University of Western Australia, 35 Stirling Highway, Crawley, Western Australia, 6009, Australia.
The isomerization of internal alkynes ArC≡CAr within the coordination environment of low-valent half-sandwich [Ru(dppe)Cp] complexes via a 1,2-migration process affords vinylidene species [Ru{=C=C(Ar)Ar}(dppe)Cp]. The rearrangement reactions of symmetrically and asymmetrically substituted substrates featuring different electron-donating and -withdrawing groups and of varying steric bulk were modelled using density functional theory (DFT), and the conclusions supported by experimental observations. Examination of the reaction pathway and associated activation barriers reveal a high solvent dependency for the generation of the key intermediate species [Ru(dppe)Cp] from [RuCl(dppe)Cp] by halide dissociation in the presence of Na salts of weakly coordinating anions, with the lattice enthalpy of the NaCl by-product playing a critical role in the overall thermochemical balance of the reaction.
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