Synthesis and spectroscopic properties of iminosilanes

Herbig, Marcus; Kroke, Edwin

doi:10.1016/j.cdc.2023.100992

Cited by 1 publication

(10 citation statements)

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“…Table S1). NMR spectra (of CDCl 3 solutions with tetramethylsilane, TMS, as an internal standard) were recorded either on a BRUKER DPX 400 spectrometer (Bruker Biospin, Rheinstetten/Karlsruhe, Germany) at 400.13 MHz, 100.61 MHz, and 79.49 MHz or on a BRUKER AVANCE III 500 MHz spectrometer (Bruker Biospin, Rheinstetten/Karlsruhe, Germany) at 500.13 MHz, 125.76 MHz, and 99.36 MHz for 1 H, 13 C, and 29 Si, respectively. The spectra are shown in the supporting information (Figures S1-S15).…”

Section: General Considerationsmentioning

confidence: 99%

“…The device works with an air-cooled Nd:YAG-Laser with a wavelength of 1064 nm and a nitrogen-cooled detector. The samples (dried in vacuo; according to 1 H and 13 C NMR, they were devoid of solvent of crystallization) were filled in glass tubes and sealed with PTFE-paste. The intensity is listed as follows: vs (very strong) 80-100% of the highest signal, followed by s (strong), m (medium), w (weak), and vw (very weak), descending further in intensity in 20% increments with respect to the strongest signal.…”

Section: General Considerationsmentioning

confidence: 99%

“…A product of sufficient purity (according to NMR spectroscopy) was obtained along an analogous route using excess triethylamine and chlorotrimethylsilane: 4.38 g (46 mmol) 2-aminopyrimidine, 7.35 g (72 mmol) triethylamine, and 7.75 g (71 mmol) chlorotrimethylsilane yielded 5.25 g (31 mmol, 68%,) of 1. Melting point: 58 4,6 ); 13 C NMR (CDCl 3 , 100 MHz): δ (ppm) −0.4 (SiMe 3 ), 111.1 (C 5 ), 157.9 (C 4,6 ), and 164.5 (C 2 ); and 29 Si NMR (CDCl 3 , 79 MHz): δ (ppm) 4.7.…”

Section: Syntheses and Characterizationmentioning

confidence: 99%

“…To remove traces of THF, the product was recrystallized from CHCl 3 . Melting point: 134 13 C NMR (CDCl 3 , 100 MHz) δ (ppm) −1.0 (SiMe 2 ), 111.4 (C 5 ), 157.9 (C 4,6 ), and 164.1 (C 2 ); and 29 Si NMR (CDCl 3 , 79 MHz): δ (ppm) −5.6.…”

Section: Syntheses and Characterizationmentioning

confidence: 99%

“…The insertion of heteroallenes into Si-N bonds may also serve as an entry into silicon coordination chemistry (i.e., the syntheses of Si compounds with hexa-or pentacoordinate Si atom, VI [10] and VII [11], respectively). As part of those studies and of related investigations in our group, we synthesized a portfolio of aminosilanes and other compounds with Si-N bond(s), including silylated amines [6,9,12], imines [13], and cyclic aminosilanes [14], and explored their reactions with CO 2 or isocyanates. In addition, we have already investigated the reactivity of silyl morpholine towards a variety of heteroallenes [15].…”

Section: Introductionmentioning

confidence: 99%

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Molecular Structures and Intermolecular Hydrogen Bonding of Silylated 2-Aminopyrimidines

2023

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A series of silylated 2-aminopyrimidines Me(4−n)Si(NHpyr)n (Me = methyl, NHpyr = pyrimid-2-ylamino, n = 1, 2, 3, 4), i.e., compounds 1, 2, 3, and 4, respectively, was prepared from a series of the respective chlorosilanes Me(4−n)SiCln and 2-aminopyrimidine. Triethylamine was used as a sacrificial base. Compounds 1, 2, 3, and 4 are solid at room temperature. They were analyzed using 1H, 13C, 29Si NMR, and Raman spectroscopy, and their molecular structures were confirmed by single-crystal X-ray diffraction analyses. All structures exhibit intramolecular van der Waals contacts between the silicon atom and one nitrogen atom of the pyrimidine moiety. Thus, their Si coordination spheres can be interpreted as [4+n] coordinated capped tetrahedra. Intermolecular hydrogen bonds (N–H···N bridges between the Si-bound amino groups and the non-Si-capping pyrimidine N atoms) are a constant contributor to the solid-state structures of these compounds. Furthermore, compounds 2 and 4 exhibit N–H···N bridges which involve 50% of their Si-capping N atoms as hydrogen bridge acceptors. Consequently, 50% of the non-Si-capping pyrimidine N atoms are stabilized by C–H···N contacts. As a result of a particularly dense network of intermolecular hydrogen bridges, the melting point of Si(NHpyr)4 (compound 4) is higher than 300 °C.

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Section: General Considerationsmentioning

confidence: 99%

Section: General Considerationsmentioning

confidence: 99%