Less than ten years of acquaintance with hypercoordinated silicon derivatives in our lab is described in this account. Martin's spirosilane derivatives open new opportunities as ligands and as agents for the activation of small molecules and bis-catecholato silicates have proven to be exquisite radical precursors in photoredox conditions for broad synthetic applications.
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http://dx.doi.org/10.1002/tcr.202100049 | DOI Listing |
Angew Chem Int Ed Engl
October 2024
Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130023, China.
Photoelectron spectroscopy and theoretical calculations have identified the global minimum structure of the 16-valence electron SiCu cluster, which features a planar tetracoordinate silicon (ptSi) in a rhombic arrangement. The Si and Cu triangles are interconnected by a Si/Cu edge, forming an ordered chain-like structure. Besides the conventional 2c-2e σ-bond connecting Si and Cu, the stability of this cluster is reinforced by a delocalized 3c-2e σ-bond in Cu and a π-bond in Si.
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November 2023
Institut für Anorganische Chemie, TU Bergakademie Freiberg, D-09596 Freiberg, Germany.
In chloroform solution, the reaction of bis(tert-butylamino)dimethylsilane ((BuNH)SiMe) and an α-amino acid (α-amino isobutyric acid, ; D-phenylglycine, ; L-valine, ) in the presence of -methylimidazole (NMI) gave rise to the formation of the pentacoordinate silicon complexes , and , respectively. Therein, the amino acid building block was a di-anionic bidentate chelator at the silicon atom. In solution, the complexes were involved in rapid coordination-dissociation equilibria between the pentacoordinate Si complex (e.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2023
Institüt für Anorganische Chemie, Universität Göttingen, Tammannstraße 4, 37077, Göttingen, Germany.
Discovering new bonding scenarios and subsequently exploring the reactivity contribute substantially to advance the main group element chemistry. Herein, we report on the isolation and characterization of an intriguing class of the hydrido-benzosiloles 2-4. These compounds exhibit a side arm of the amidinatosilylenyl group, featuring unidirectional silicon(II)/silicon(IV) donor-acceptor interaction on account of the geometric constraint.
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November 2023
Department of Chemistry, University of Vermont, 82 University Place, 05405, Burlington, VT, USA.
Group I alkoxides are highly active precatalysts in the heterodehydrocoupling of silanes and amines to afford aminosilane products. The broadly soluble and commercially available KO Amyl was utilized as the benchmark precatalyst for this transformation. Challenging substrates such as anilines were found to readily couple primary, secondary, and tertiary silanes in high conversions (>90 %) after only 2 h at 40 °C.
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July 2023
UMR 6226-Institute of Chemical Sciences of Rennes, University of Rennes, 35042 Rennes, France.
Electrochemical oxidation of 1-R-substituted silatranes (R = Me, vinyl, (CH)CN, CHPh, CH(CH), Ph, CHMe, -Cl-CH, Cl)-classical representatives of pentacoordinated silicon compounds-and the formation of their short living cation radicals upon reversible or quasi-reversible one-electron withdrawal were studied by means of cyclic and square-wave voltammetry, faradaic impedance spectroscopy and real-time temperature-dependent EPR spectroelectrochemistry supported by DFT B3PW91/6-311++G(d,p) (C-PCM, acetonitrile) calculations. The main reaction responsible for the decay of is shown to be their deprotonation, and ways of increasing the stability of these species are proposed.
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