Search results for "Silylene"
showing 10 items of 13 documents
A three-coordinate iron–silylene complex stabilized by ligand–ligand dispersion forces
2016
The structural and bonding properties of a three-coordinate N-heterocyclic silyene (NHSi) complex of the iron(II) amide [Fe{N(SiMe3)2}2] are reported. Computational studies reveal that dispersion forces between the amido SiMe3 substituents and the isopropyl substituents on the NHSi ligand significantly enhance the stability of the complex, along with Fe-to-Si π-backbonding.
Reactions of Alkenes and Alkynes with an Acyclic Silylene and Heavier Tetrylenes under Ambient Conditions
2014
Cycloaddition reactions of the acyclic silylene Si(SAriPr4)2 (AriPr4 = C6H3-2,6(C6H3-2,6-iPr2)2) with a variety of alkenes and alkynes were investigated. Its reactions with the alkynes phenylacetylene and diphenylacetylene and the diene 2,3-dimethyl-1,3-butadiene yielded silacycles (AriPr4S)2tiebar above startSi(CH═tiebar above endCPh) (1), (AriPr4S)2tiebar above startSi(PhC═tiebar above endCPh) (2), and (AriPr4S)2tiebar above startSiCH2CMeCMetiebar above endCH2 (3) at ambient temperature. The compounds were characterized by X-ray crystallography, 1H, 13C, and 29Si NMR spectroscopy, and IR spectroscopy. No reaction was observed with more substituted alkenes such as propene, (Z)-2-butene, te…
Reversible complexation of ethylene by a silylene under ambient conditions.
2014
Treatment of toluene solutions of the silylenes Si(SArMe6)2 (ArMe6 = C6H3-2,6(C6H2-2,4,6-Me3)2, 1) or Si(SArPri4)2 (ArPri4 = C6H3-2,6(C6H3-2,6-Pri2)2, 2) with excess ethylene gas affords the siliranes (ArMe6S)2tiebar above startSiCH2tiebar above endCH2 (3) or (ArPri4S)2tiebar above startSiCH2tiebar above endCH2 (4). Silirane 4 evolves ethylene spontaneously at room temperature in toluene solution. A Van’t Hoff analysis by variable-temperature 1H NMR spectroscopy showed that ΔGassn = −24.9(2.5) kJ mol–1 for 4. A computational study of the reaction mechanism using a model silylene Si(SPh)2 (Ph = C6H5) was in harmony with the Van’t Hoff analysis, yielding ΔGassn = −24 kJ mol–1 and an activatio…
CCDC 751851: Experimental Crystal Structure Determination
2010
Related Article: M.Wilfling, K.W.Klinkhammer|2010|Angew.Chem.,Int.Ed.|49|3219|doi:10.1002/anie.200905950
CCDC 751854: Experimental Crystal Structure Determination
2010
Related Article: M.Wilfling, K.W.Klinkhammer|2010|Angew.Chem.,Int.Ed.|49|3219|doi:10.1002/anie.200905950
CCDC 864639: Experimental Crystal Structure Determination
2012
Related Article: B.D.Rekken, T.M.Brown, J.C.Fettinger, H.M.Tuononen, P.P.Power|2012|J.Am.Chem.Soc.|134|6504|doi:10.1021/ja301091v
CCDC 247552: Experimental Crystal Structure Determination
2005
Related Article: K.W.Klinkhammer, Yun Xiong, Shenglai Yao|2004|Angew.Chem.,Int.Ed.|43|6202|doi:10.1002/anie.200461670
CCDC 751850: Experimental Crystal Structure Determination
2010
Related Article: M.Wilfling, K.W.Klinkhammer|2010|Angew.Chem.,Int.Ed.|49|3219|doi:10.1002/anie.200905950
CCDC 751852: Experimental Crystal Structure Determination
2010
Related Article: M.Wilfling, K.W.Klinkhammer|2010|Angew.Chem.,Int.Ed.|49|3219|doi:10.1002/anie.200905950
Probing the non-innocent nature of an amino-functionalised β-diketiminate ligand in silylene/iminosilane systems.
2020
Electron-rich β-diketiminate ligands, featuring amino groups at the backbone β positions (“N-nacnac” ligands) have been employed in the synthesis of a range of silylene (SiII) complexes of the type (N-nacnac)SiX (where X = H, Cl, N(SiMe3)2, P(SiMe3)2 and Si(SiMe3)3). A combination of experimental and quantum chemical approaches reveals (i) that in all cases rearrangement to give an aza-butadienyl SiIV imide featuring a contracted five-membered heterocycle is thermodynamically favourable (and experimentally viable); (ii) that the kinetic lability of systems of the type (N-nacnac)SiX varies markedly as a function of X, such that compounds of this type can be isolated under ambient conditions …