ChemInform Abstract: DIE RK. VON TRIAETHOXYSILAN MIT ALLYLAMIN IN GEGENWART VON KATALYSATOREN

Belyakova, Z. V.; Bochkarev, V. N.; Golubtsov, S. A.; Belikova, Z. V.; Yamova, M. S.; Ainshtein, A. A.; Baranova, G. G.; Efremova, L. A.; Popkov, K. K.

doi:10.1002/chin.197232330

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“…Small (<5%), yet detectable, amounts of 1-silyl-1-octene, arising from dehydrogenative silylation, were also observed by gas chromatography and NMR spectroscopy. No catalytic turnover was observed with (EtO) 3 SiH due to competing redistribution of the silane to (EtO) 4 Si (and likely SiH 4 ) under catalytic conditions. , No catalytic activity was observed with the pyridine bis(oxazoline) iron dialkyl complex, ( R , R )-( i Pr Pybox)Fe(CH 2 SiMe 3 ) 2 .…”

Section: Resultssupporting

confidence: 70%

Synthesis, Electronic Structure, and Alkene Hydrosilylation Activity of Terpyridine and Bis(imino)pyridine Iron Dialkyl Complexes

et al. 2012

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Iron dialkyl complexes, [N 3 ]Fe(CH 2 SiMe 3 ) 2 , with three different classes of tridentate, nitrogen-based "[N 3 ]" ligands, aryl-substituted bis(imino)pyridines, terpyridine, and pyridine bis(oxazoline), have been synthesized and evaluated in the catalytic hydrosilylation of olefins with tertiary silanes. The 2,2′:6′,2″-terpyridine (terpy) complex, (terpy)Fe-(CH 2 SiMe 3 ) 2 , was prepared either via alkylation of (terpy)-FeCl 2 with LiCH 2 SiMe 3 or by pyridine displacement from (pyridine) 2 Fe(CH 2 SiMe 3 ) 2 by free terpyridine. The arylsubstituted bis(imino)pyridine compounds, ( R PDI)Fe(CH 2 SiMe 3 ) 2 ( R PDI = 2,6-(2,6-R 2 -C 6 H 3 NCMe) 2 C 5 H 3 N), with smaller 2,6-dialkyl substituents (R = Et, Me) or a 2-i Pr substituent ( 2-iPr PDI)Fe(CH 2 SiMe 3 ) 2 ( 2-iPr PDI = 2,6-(2-i Pr-C 6 H 4 N CMe) 2 C 5 H 3 N, are effective precursors (0.5 mol %) for the anti-Markovnikov hydrosilylation of 1-octene with (Me 3 SiO) 2 MeSiH and (EtO) 3 SiH over the course of 1 h at 60 °C. No hydrosilylation activity was observed with Et 3 SiH. The most hindered member of the series, ( iPr PDI)Fe(CH 2 SiMe 3 ) 2 , and the pyridine bis(oxazoline) iron compound, (R,R)-( iPr Pybox)Fe(CH 2 SiMe 3 ) 2( iPr Pybox = 2,6-bis[isopropyl-2-oxazolin-2-yl]pyridine), were inactive for the hydrosilylation of 1-octene with all tertiary silanes studied. By contrast, the terpyridine precursor, (terpy)Fe(CH 2 SiMe 3 ) 2 , reached >95% conversion at 60 °C with Et 3 SiH and (Me 3 SiO) 2 MeSiH. In addition, the hydrosilylation of vinylcyclohexene oxide was accomplished in the presence of 1.0 mol % (terpy)Fe(CH 2 SiMe 3 ) 2 , demonstrating functional group compatibility unique to this compound that is absent from bis(imino)pyridine iron compounds. The electronic structures of all three classes of iron dialkyl compounds have been evaluated by a combination of X-ray diffraction, magnetochemistry, Mossbauer spectroscopy, and density functional theory calculations. All of the compounds are best described as high-spin iron(III) compounds with antiferromagnetic coupling to chelate radical anions.

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Section: Resultssupporting

confidence: 70%

Synthesis, Electronic Structure, and Alkene Hydrosilylation Activity of Terpyridine and Bis(imino)pyridine Iron Dialkyl Complexes

et al. 2012

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ChemInform Abstract: DIE RK. VON TRIAETHOXYSILAN MIT ALLYLAMIN IN GEGENWART VON KATALYSATOREN

Abstract: Die Addition von Triäthoxysilan (I) an Allylamin (II) in Gegenwart von Hexachlorplatinsäure bei 125°C liefert 51% γ‐Aminopropyl‐(III) und 11% β‐Aminoisopropyltriäthoxysilan (IV).

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Synthesis, Electronic Structure, and Alkene Hydrosilylation Activity of Terpyridine and Bis(imino)pyridine Iron Dialkyl Complexes

Synthesis, Electronic Structure, and Alkene Hydrosilylation Activity of Terpyridine and Bis(imino)pyridine Iron Dialkyl Complexes

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