Reactions of dihydrofurylsilanes with O- and N-nucleophiles

Crystal structures and Hirshfeld surface analyses of bis(4,5-dihydrofuran-2-yl)dimethylsilane and (4,5-dihydrofuran-2-yl)(methyl)diphenylsilane

“…t-butanol) and N-nucleophiles [e.g. LiN(Et) 2 ] (Lukevics et al, 1997). By means of this efficient pathway, a noteworthy approach to pentacoordinated organyl silatranes has been made (Gevorgyan et al, 1997), as well as for (-aminomethyl)silanes (Labrecque et al, 1994).…”

Effect of proton donors on the intramolecular coordination C=O→Si-F in (acyloxymethyl)trifluorosilanes.Ab initio,DFT and FTIR study, QTAIM analysis

“…[1][2][3][4][5][6][7][8][9] Phenyl-, hexyl-, pentafluorophenyl-and (phenylethynyl)trifluorosilanes having tetracoordinated silicon atom form complexes with pyridine (of 1:1 and 1:2 composition), 2,2′-bipyridine and 1,10-phenanthroline (of 1:1 composition) in which the silicon atom is penta-or hexacoordinated. [7][8][9] (Aroyloxymethyl)trifluorosilanes, which are typical compounds of pentacoordinate silicon with intramolecular coordination bond C=O→Si, [10][11][12][13] also form two types of stable complexes with pyridine having hexacoordinate silicon atom: 1:1 complexes having the retained intramolecular coordination bond C=O→Si and the newly formed intermolecular bond N→Si, and 1:2 complexes having two newly formed intermolecular bonds N→Si and lacking the intramolecular bond C=O→Si. [1][2][3][4]9] With bidentate nitrogen-containing bases, like TMEDA, 2,2′-bipyridine and 1,10-phenanthroline, (aroyloxymethyl)trifluorosilanes form only complexes of 1:1 composition having hexacoordinate silicon atom.…”

“…[15][16][17][18][19] There are at least two reasons for such interest: first, a plethora of intramolecular silicon complexes show substantial variation of the IR and NMR spectroscopic characteristics of the coordination site as a function of the aggregate state, temperature and the nature of the solvent. [10][11][12][13][20][21][22][23][24][25] Second, since chemical reactions are mostly carried out in solution, understanding of the processes occurring upon interaction of the molecules of organyltrifluorosilanes with the solvent will promote the progress of synthetic chemistry and materials based on organosilicon compounds. Protophilic solvents acting as lone electron pair (LP) donors were shown to form solvate complexes with (4-nitrobenzoyloxymethyl)trifluorosilane, in which the coordination number of the silicon atom is extended to six with retention of the C=O→Si bond.…”

“…[15] No literature data are available on the interaction of (acyloxymethyl)trifluorosilanes with proton donors, although their high hydrolytic stability with respect to organyltrifluorosilanes having tetracoordinate silicon atom was noted. [10][11][12][13] This is somewhat surprising, since the compounds of hypervalent silicon normally show enhanced reactivity in reactions with both electrophiles and nucleophiles. [10][11][12][13][20][21][22][23][24][25][26][27] A hydrolysis reaction is not an exception; according to theoretical and experimental data, the pentacoordinated silicon compounds with different types of coordination (silatranes and O→Si chelates), including pentacoordinated fluorosilanes, react with water.…”

“…[10][11][12][13] This is somewhat surprising, since the compounds of hypervalent silicon normally show enhanced reactivity in reactions with both electrophiles and nucleophiles. [10][11][12][13][20][21][22][23][24][25][26][27] A hydrolysis reaction is not an exception; according to theoretical and experimental data, the pentacoordinated silicon compounds with different types of coordination (silatranes and O→Si chelates), including pentacoordinated fluorosilanes, react with water. [28][29][30][31][32][33][34][35][36][37][38][39][40][41][42] N-(Silylmethyl)phosphoramides R 2 P(O)NR′CH 2 SiMe 3-n Hal n having relatively weak coordination bond P=O→Si (2.1 < d SiO < 2.7 Å) give complexes with chloroform.…”