Structure and Reactivity of 1-Isothiocyanatosilatrane:  The First Silatrane with a Direct Si−NCS Bond

Narula, Suraj P.; Shankar, Ravi; Kumar, Manish; Chadha, Raj K.; Janaik, Christopher

doi:10.1021/ic960695y

Cited by 41 publications

(25 citation statements)

References 32 publications

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“…The SiÀNCS bond length in 1-(thiocyanato-N)silatrane [10] (1.800 (3) ) is similar to that of the axial SiÀNCS distance in 9 (1.7985 (13) ). However, in contrast to compound 9, where Si-N-C angles of 162.01(12)8 (axial) and 160.72(12)8 (equatorial) are observed, the SiÀNCS moiety of 1-(thiocyanato-N)silatrane is reported to be almost linear (Si-N-C 174.7(3)8) [10] (for computational studies of 1-(thiocyanato-N)silatrane, see reference [11]). …”

Section: Crystal Structure Analysesmentioning

confidence: 66%

Synthesis and Structural Characterization of Neutral Higher‐Coordinate Silicon(iv) Complexes with Tridentate Dianionic Chelate Ligands

Seiler

Burschka

Metz

et al. 2005

Chemistry A European J

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The neutral pentacoordinate silicon(IV) complexes 8 and 9 with an SiO2N3 skeleton and the neutral hexacoordinate silicon(IV) complex 10.1/2 CH3CN with an SiO4N2 skeleton were synthesized, starting from tetra(cyanato-N)silane or tetra(thiocyanato-N)silane. Compounds 8 and 9 contain one tridentate dianionic ligand derived from 4-[(2-hydroxyphenyl)amino]pent-3-en-2-one and two monodentate singly charged cyanato-N or thiocyanato-N ligands bound to the silicon(IV) coordination center, whereas the silicon(IV) center of 10 is coordinated by two of these tridentate dianionic ligands. All compounds were characterized by single-crystal X-ray diffraction and solid-state and solution NMR spectroscopy. To get more information about the stereochemistry of the compounds studied, the experimental investigations were complemented by computational studies.

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Section: Crystal Structure Analysesmentioning

confidence: 66%

Synthesis and Structural Characterization of Neutral Higher‐Coordinate Silicon(iv) Complexes with Tridentate Dianionic Chelate Ligands

Seiler

Burschka

Metz

et al. 2005

Chemistry A European J

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“…The longest Si N bond (2.89Å 156 ) is found for the silatranylplatinum complex 39, which should be classified as a 'quasisilatrane' 27 . The transannular bond of 2.007Å in 1-isothiocyanatosilatrane 29 68 is the shortest reported so far in neutral silatranes. In silatranyl oxonium salts 36 the Si N bond is a record short value, 1.965Å 150 .…”

Section: Molecular Structurementioning

confidence: 81%

“…ROSi(OCH 2 CH 2 ) 3 N ROH + (R′O) 4 Si + THEA R = Alk, cyclo-Alk, ArCH 2 64 , Ar 33,65,66 ; R′ = MeO, EtO (11) The classical way shown in equation 2 was used to prepare silatranes having a labile exocyclic S Si bond (equation 12) 67 or a pseudohalogen function at the silicon (equation 13) 68 .…”

Section: Formation From Organyltrialkoxysilanesmentioning

confidence: 99%

Silatranes and Their Tricyclic Analogs

Pestunovich

Kirpichenko

Воронков

1998

PATAI'S Chemistry of Functional Groups

144

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“…Other starting materials such as silicon(IV) chloride (Aldrich AR grade), absolute alcohol (Bengal chemicals), 2,4-dimethyl phenol (E-Merck), hexamethylene tetramine (Aldrich) and potassium thiocyanate (E-Merck) were used as supplied. Tris-(2-hydroxy-3,5-dimethyl benzyl)amine [2], dimethyl sulfite [8], methyl methanesulfonate [9], triethoxyisothiocyanatosilane [7], 1-isothiocyanato six membered ring silatrane [1] and 1-isothiocyanato five membered ring silatrane [10] were synthesized according to procedure reported earlier. Solvents were purified according to standard procedures [11].…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Characterization of Novel 1-Methanesulfonato Silatranes

Singh¹

2014

IJIRSET

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CH 3 (O) 2 SOSi(OC 6 H 2 Me 2 CH 2 ) 3 N (1), CH 3 OSi(OC 6 H 2 Me 2 CH 2 ) 3 N (2) and CH 3 (O) 2 SO.Si(OCH 2 CH 2 ) 3 N (3) have been synthesized in high yield by the reaction of 1-isothiocyanato-silatranes with dimethyl sulfite and methyl methanesulfonate. These novel silatranes have been characterized by elemental analysis, infrared spectroscopy, 1 H, 13 C, 29 Si NMR spectroscopy and mass spectrometry. Semi-empirical quantum mechanical calculations were done to study the N→Si transannular bond length. KEY WORDS:Six membered silatrane, Methane sulfonato silatrane, Pentacoordinated silicon, Hypervalent compound, Five membered silatranes I. INTRODUCTIONSilatranes containing six-membered ring were synthesized as reported in literature [1][2]. It was shown that the silatrane systems with the larger rings allowed substituent effects associated with the axial position of the resulting trigonal bipyramidal structures (tbp) to be reflected in dramatically altering the Si-N bond interactions as well as in changes of the 29 Si chemical shifts [3][4][5][6][7]. The use of dimethyl sulfite and methyl methanesulfonate as alkylating, alkoxylating and acetylating reagent in synthesis is well known in literature [8,9]. To my knowledge these are the first of type of silatrane containing1-methane sulfonato as exocyclic group to silicon in silatranes. In order to understand the reactivity of 1-Isothiocyanatosilatranes with dimethyl sulfite & methyl methane sulfonate, a detailed study of this reaction was undertaken. II. EXPERIMENTALAll operations were carried out under dry nitrogen atmosphere. Solvents were freshly distilled under an inert atmosphere from sodium and sodium benzophenone (hexane), (tetrahydrofuran, diethylether) and phosphorus pentaoxide (acetonitrile and dichloromethane) before use. Bases such as triethanol amine (Aldrich) were refluxed over potassium hydroxide pellets and distilled under dry nitrogen atmosphere before use. Other starting materials such as silicon(IV) chloride (Aldrich AR grade), absolute alcohol (Bengal chemicals), 2,4-dimethyl phenol (E-Merck), hexamethylene tetramine (Aldrich) and potassium thiocyanate (E-Merck) were used as supplied. 29 Si NMR (59.60 MHz) spectra were obtained on JEOL AL 300 instrument. Chemical shifts were reported with respect to TMS as external standard. Mass spectral measurements (EI, 70ev) were carried out with VG Analytical (70-S) spectrometer. The elemental analysis were performed using PERKIN-ELMER (model 2400) C, H, N analyzer. The content of sulfur and silicon was determined by standard gravimetric methods.

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Structure and Reactivity of 1-Isothiocyanatosilatrane: The First Silatrane with a Direct Si−NCS Bond

Cited by 41 publications

References 32 publications

Synthesis and Structural Characterization of Neutral Higher‐Coordinate Silicon(iv) Complexes with Tridentate Dianionic Chelate Ligands

Synthesis and Structural Characterization of Neutral Higher‐Coordinate Silicon(iv) Complexes with Tridentate Dianionic Chelate Ligands

Silatranes and Their Tricyclic Analogs

Synthesis and Characterization of Novel 1-Methanesulfonato Silatranes

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