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The solid and solution state structure of the vanadium(ii) N-heterocyclic silylene (NHSi) complex, [(IPr)V(Cp)] (1) is reported (IPr: 1,3-bis(2,6-diisopropylphenyl)-1,3-diaza-2-silacyclopent-4-en-2-ylidene). The electronic structure of 1 is probed using a combination of magnetic measurements, EPR spectroscopy and computational studies. The V-Si bond strength and complex forming mechanism between vanadocene and an NHSi ligand is elucidated using computational methods.
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http://dx.doi.org/10.1039/c7dt01226h | DOI Listing |
Chem Sci
August 2025
Department of Chemistry, Indian Institute of Science Education and Research Pune Dr Homi Bhabha Road, Pashan Pune-411008 India
Anchoring homolytic and heterolytic bond functionalisation at low-coordinate coinage metal centres is important due to their potential use as active catalysts in organic transformations. In the realm of carbene-stabilised coinage metal chemistry, heteroatom functionalised coinage metal precursors synthesised from such bond activations have long been explored. Interestingly, -heterocyclic silylene, being an equally potent neutral donor ligand, has not been used for the same.
View Article and Find Full Text PDFACS Omega
February 2025
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati, Tirupati 517619, Andhra Pradesh, India.
Herein, we depict the detailed computational studies on the stability and chemical bonding of heteronuclear 1,2-dichloro-silylene-germylenes [(Cl)SiGe(Cl)] supported by homoleptic [L = L' = cAAC; NHC; and PMe] and heterobileptic [L, L' = cAAC; NHC; cAAC, PMe; NHC; and PMe] donor base ligands with the general formula (L)(Cl)SiGe(Cl)(L') having tunable binding energies. The bonding of the corresponding didehalogenated analogue, (L)SiGe(L') has been also investigated to explore the possibility of multiple bonding between the two-coordinate heteroatoms, Si and Ge. Our studies employing density functional theory, atoms in molecules analysis, and energy decomposition analysis coupled with natural orbitals for chemical valence (EDA-NOCV) unveiled the synthetic viability of the hypothetical compounds in the presence of phosphines and/or stable singlet carbenes, e.
View Article and Find Full Text PDFChemistry
February 2025
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai, 980-8578, Japan.
Reactions of cyclic thioureas (1,3,4,5-tetramethylimidazol-2-thione and 1,3-dimethylimidazolidin-2-thione) and ureas (1,3,4,5-tetramethylimidazol-2-one and 1,3-dimethylimidazolidin-2-one) with an isolable dialkylsilylene were examined. In these reactions, cyclic thioureas served as sulfur and NHC (N-heterocyclic carbene) sources, and the corresponding silanethione and NHC-derived products formed via silanethione-NHC complexes. Reactions of cyclic ureas with the silylene afforded a new NHC and an isolable azomethine ylide.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
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 Science Education and Research Pune, Dr. Homi Bhabha Road, Pashan, Pune, 411008, India.
We have explored NHSi-supported copper(I) complexes as active and highly efficient catalysts for A (aldehyde-alkyne-amine) and KA (ketone-alkyne-amine) three-component coupling reactions to synthesize propargyl amines in excellent yields with high TOF under solvent-and additive-free conditions.
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