Progressions in hyper–coordinate silicon complexes

Singh, Gurjaspreet; Kaur, Gurpreet; Singh, Jandeep

doi:10.1016/j.inoche.2017.12.002

Cited by 33 publications

(5 citation statements)

References 110 publications

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“…Even though ammonia remained a scarcely encountered ligand in silicon coordination chemistry, various other N-donor molecules were found capable of binding to silanes with electronegative substituents and thus enhancing the Si coordination number, e.g., in the adduct SiCl 4 (pyridine) 2 [2]. The use of chelating ligands enhanced the variety of N-donors ligands, which thus formed penta-or hexacoordinate Si-compounds, and various reviews (e.g., [3][4][5][6][7][8]) provide insights into the wealth of silicon coordination chemistry with additional N-donors or with various other ligands. In this context, α-amino acids represent a class of chelators with N-donor functionality, which should be suitable to bind to silicon in a chelating manner (with the formation of five-membered rings, a common motif in Si-coordination chemistry), to enhance the Si coordination number.…”

Section: Introductionmentioning

confidence: 99%

Lewis Acid-Base Adducts of α-Amino Acid-Derived Silaheterocycles and N-Methylimidazole

Seidel,

Gericke,

Kutzner

et al. 2023

Molecules

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In chloroform solution, the reaction of bis(tert-butylamino)dimethylsilane ((tBuNH)2SiMe2) and an α-amino acid (α-amino isobutyric acid, H2Aib; D-phenylglycine, H2Phg; L-valine, H2Val) in the presence of N-methylimidazole (NMI) gave rise to the formation of the pentacoordinate silicon complexes (Aib)SiMe2-NMI, (Phg)SiMe2-NMI and (Val)SiMe2-NMI, 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.g., (Aib)SiMe2-NMI) and its constituents NMI and a five-membered silaheterocycle (e.g., (Aib)SiMe2), as shown by 29Si NMR spectroscopy. The energetics of the Lewis acid-base adduct formation and the competing solvation of the NMI molecule by chloroform were assessed with the aid of computational methods. In CDCl3 solution, deuteration of the silaheterocycle NH group proceeded rapidly, with more than 50% conversion within two days. Upon cooling to −44 °C, the chloroform solvates of the adducts (Aib)SiMe2-NMI and (Phg)SiMe2-NMI crystallized from their parent solutions and allowed for their single-crystal X-ray diffraction analyses. In both cases, the Si atom was situated in a distorted trigonal bipyramidal coordination sphere with equatorial Si–C bonds and an equatorial Si–N bond (the one of the silaheterocycle). The axial positions were occupied by a carboxylate O atom of the silaheterocycle and the NMI ligand’s donor-N-atom.

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Section: Introductionmentioning

confidence: 99%

Lewis Acid-Base Adducts of α-Amino Acid-Derived Silaheterocycles and N-Methylimidazole

Seidel,

Gericke,

Kutzner

et al. 2023

Molecules

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“…Further, owing to hydrolytically stable nature, it regulates the hydrolysis rate and condensation processes in the eld of sol-gel processes. Moreover, silatranes are also used as adhesive promoter and strong reducing agent for conversion in organic synthesis [21][22][23][24][25][26][27][28][29][30][31][32].…”

Section: Introductionmentioning

confidence: 99%

Design, Synthesis, Drug-Likeness and In Silico Prediction of Polycyclic Aromatic Schiff base Tethered Organosilatranes

Singh

Shilpy

Singh³

et al. 2022

Silicon

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The present article includes the generation of aromatic Schiff base tethered organosilatranes via two step synthetic pathways starting from anthracene-10-carbaldehyde and 1H-indole-3-carbaldehyde. The synthesis was achieved by employing condensation reaction followed by transesteri cation methodology. The prepared organosilatranes containing aromatic schiff based ligands were structurally authenticated using spectroscopic techniques such as FT-IR, NMR and mass analysis. The prepared compounds were also scrutinized for in silico physiochemical properties via Molininspiration and ADMET software and the results revealed their good biological potential for drug discovery.

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“…Silicates with five organic substituents are remarkably stable compounds. [1][2][3] Their stabilization is typically attributed to the electron withdrawing nature of the organic ligands or the coordinating heteroatoms, [4] which are often oxygen and/or nitrogen atoms (e.g., 1; Scheme 1), but silicates carrying only carbon groups can also be quite stable (m.p. > 150°C), provided the presence of two aromatic bidentate ligands as in 2a.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Conformational Behavior in Stable Pentaorganosilicates

et al. 2019

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Silicates with five organic groups are conformationally dynamic even with two bidentate ligands. Symmetry breaking by incorporating a single nitrogen or phosphorus atom provides insight into their dynamic behavior. N‐containing silicates with bidentate 2‐phenylpyridine, biphenyl, and a Me (8), Et (9) or Ph (10) ligand were studied comprehensively by NMR spectroscopy and DFT theory to reveal two isoenergetic conformers with a barrier of ca. 10 kcal mol–1. P‐containing silicate 14 with bidentate triphenylphosphane, biphenyl, and Me ligands is subject to multiple Berry pseudorotations, turnstile rotations, and conformational flexibility of the P‐center. The stability increased by masking the P‐center with a BH3 group (16). DFT and NMR modeling reveal two isoenergetic conformers for 16 with a barrier of ca. 19 kcal‧mol–1 for a complex interconversion pathway. This barrier bodes well for the design of configurationally stable chiral‐at‐metal transition metal catalysts.

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Progressions in hyper–coordinate silicon complexes

Cited by 33 publications

References 110 publications

Lewis Acid-Base Adducts of α-Amino Acid-Derived Silaheterocycles and N-Methylimidazole

Lewis Acid-Base Adducts of α-Amino Acid-Derived Silaheterocycles and N-Methylimidazole

Design, Synthesis, Drug-Likeness and In Silico Prediction of Polycyclic Aromatic Schiff base Tethered Organosilatranes

Dynamic Conformational Behavior in Stable Pentaorganosilicates

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