Complexation of tris(pentafluorophenyl)silanes with neutral Lewis bases

Dilman, Alexander D.; Levin, Vitalij V.; Korlyukov, Alexander A.; Belyakov, Pavel A.; Стручкова, Марина И.; Antipin, M. Yu.; Tartakovsky, Vladimir A.

doi:10.1016/j.jorganchem.2007.12.022

Cited by 17 publications

(7 citation statements)

References 56 publications

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“…The O 2 Si unit and the planar OPO ligand form a dihedral angle of 6.66(5)°. Similar core structures are seen in a chelated (C 6 F 5 ) 3 Si salicylaldimine complex and the related triphenylpyrithione Sn derivative . In the Sn pyrithione derivative, the hydroxylamine oxygen occupies an axial position vs an equatorial position.…”

Section: Resultsmentioning

confidence: 61%

Chelation and Stereodynamic Equilibria in Neutral Hypercoordinate Organosilicon Complexes of 1-Hydroxy-2-pyridinone

Kraft

Brennessel

2013

Organometallics

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A series of neutral organosilicon compounds, R3Si(OPO) [R = Me (1), Et (2), Ph (3)], cis-R2Si(OPO)2 [R = Me (4), Et (5), iPr (6), tBu (7), Ph (9)], (CH2)3Si(OPO)2 (8), and cis-R2Si(OPO)Cl [R = Me (10), Et (11)] (OPO = 1-oxo-2-pyridinone) have been prepared and fully characterized. X-ray crystallographic analyses show 1 to be tetracoordinate, 3, 7, and 10 to be pentacoordinate, and 4, 5, 6, 8, and 9 to be hexacoordinate. In the hexacoordinate structures, a mixture of diastereomers is observed in the form of C/N site disorder in each OPO ligand. Variable-temperature 13C and 29Si NMR studies indicate reversible Si←OC bond dissociation occurring in all pentacoordinate and hexacoordinate complexes to a varying degree with greater tendency toward dissociation in hydrogen-bonding donor solvents. Significant weakening of the dative Si←OC bond in 3 is observed in the co-crystallized adduct solvate, 3•Ph3SiOH•½C5H12, providing structural evidence for the decrease in coordination number of the OPO ligand by hydrogen-bonding donors. In the hexacoordinate complexes, increasing steric bulk of ancillary ligands also was found to promote dissociation. 1H and 13C VT-NMR studies of 4, 6, 8, and 9 indicate stereoisomerization equilibria concurrent with Si←OC bond dissociation proposed to occur through trigonal bipyramidal intermediates.

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Section: Resultsmentioning

confidence: 61%

Chelation and Stereodynamic Equilibria in Neutral Hypercoordinate Organosilicon Complexes of 1-Hydroxy-2-pyridinone

Kraft

Brennessel

2013

Organometallics

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“…The Si-F distance of 156.7(1) pm is in the expected range (d(Si-F) 158.5(1) pm in Si(C 6 F 5 ) 3 F, [7] d(Si-F) 156(1) pm in SiF 4 [8] ). The F-Si-C angles are slightly more acute than the C-Si-C angles.…”

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confidence: 79%

“…In contrast to this reaction, treatment of neat Si(C 2 F 5 ) 3 Cl or Si(C 2 F 5 ) 3 Br with SbF 3 yields Si(C 2 F 5 ) 3 F [Eq. (7)] as a colorless liquid which solidifies at À110 8C. A twinned crystal was obtained by in situ crystallization of the liquid sealed in a glass capillary by manually generating a suitable seed crystal slightly below the melting point first, followed by slowly cooling to À173 8C.…”

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confidence: 99%

Synthesis of Tris‐ and Tetrakis(pentafluoroethyl)silanes

et al. 2014

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The synthesis and complete characterization of functional, highly Lewis acidic tris(pentafluoroethyl)silanes as well as tetrakis(perfluoroalkyl)silanes Si(C2F5)4 and Si(C2F5)3 CF3 by direct fluorination is described. The reaction of SiCl4 with LiC2F5 invariably affords (pentafluoroethyl)fluorosilicates. To avoid silicate formation by fluoride transfer from LiC2F5 the Lewis acidity of the silane has to be decreased by electron-donating substituents, such as dialkylamino groups. The easily accessible Si(C2F5)3 NEt2 is a valuable precursor for a series of tris(pentafluoroethyl)silanes.

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“…The Lewis acidity at silicon can be enhanced by three strategies: (1) strong electron withdrawing substituents,8 (2) incorporation of silicon in strained cycles9 or (3) transient activation via Lewis base coordination 10. For example, the use of perfluoroaryl substituents in (C 6 F 5 ) n SiF 4– n was reported by Frohn and Dilman 11. Hoge demonstrated the C 2 F 5 group as a robust substituent for the generation of strong silicon Lewis acids 13.…”

Section: Introductionmentioning

confidence: 99%