Reaction of CHI3 with six equivalents of CrCl2 in THF at low temperatures affords [Cr3Cl3(μ-Cl)3(μ3-CH)(thf)6] as the first isolable high-yield Cr III μ3-methylidyne complex. Substitution of the terminal chlorido ligands via salt metathesis with alkali-metal cyclopentadienides generates isostructural half-sandwich chromium(III)-μ3-methylidynes [Cp R 3Cr3(μ-Cl)3(μ3-CH] (Cp R = C5H5, C5Me5, C5H4SiMe3). Side and decomposition products of the Cl/Cp R exchange reactions were identified and structurally characterized for [Cr4(μ-Cl)4(μ-I)2(μ4-O)(thf)4] and [(η 5 -C5H4SiMe3)CrCl(µ-Cl)2Li(thf)2].The Cl/Cp R exchange drastically changed the ambient-temperature effective magnetic moment μeff from 9.30/9.11 μB (solution/solid) to 3.63/4.32 μB (Cp R = C5Me5). Reactions of [Cr3Cl3(μ-Cl)3(μ3-CH)(thf)6] with aldehydes and ketones produce intricate mixtures of species through oxy/methylidyne exchange, which were partially identified as radical recombination products through GC/MS analysis and 1 H NMR spectroscopy.
Treatment of Cr[N(SiMe3)2]2(thf)2 with HOSiR3 (R = Et, iPr) in THF afforded the bridged CrII siloxide complexes Cr3(OSiEt3)2(μ-OSiEt3)4(thf)2 and Cr2(OSiiPr3)2(μ-OSiiPr3)2(thf)2 in high yield. Exposure of these compounds to vacuum in...
Die Reaktion von CHI 3 mit sechs ¾quivalenten CrCl 2 in THF bei tiefen Temperaturen ergibt [Cr 3 Cl 3 (m 2 -Cl) 3 -(m 3 -CH)(thf) 6 ] als den ersten in hohen Ausbeuten isolierbaren Cr III -m 3 -Methylidinkomplex. Substitution der terminalen Chlorido-Liganden via Salzmetathese mit Alkalimetall-Cyclopentadieniden generiert die isostrukturellen Halbsandwich-Chrom(III)-m 3 -Methylidine [Cp R 3 Cr 3 (m 2 -Cl) 3 (m 3 -CH] (Cp R = C 5 H 5 , C 5 Me 5 , C 5 H 4 SiMe 3 ). Neben-und Zersetzungsprodukte des Cl/Cp R -Austausches konnten identifiziert und für [Cr 4 (m 2 -Cl) 4 (m 2 -I) 2 (m 4 -O)(thf) 4 ] und [(h 5 -C 5 H 4 SiMe 3 )CrCl(m 2 -Cl) 2 Li-(thf) 2 ] strukturell charakterisiert werden. Der Cl/Cp R -Austausch verändert das effektive magnetische Moment bei Raumtemperatur dramatisch von m eff = 9.30/9.11 m B (Lçsung/ Feststoff) zu 3.63/4.32 m B (Cp R = C 5 Me 5 ). Die Reaktionen von [Cr 3 Cl 3 (m 2 -Cl) 3 (m 3 -CH)(thf) 6 ] mit Aldehyden und Ketonen produzierten komplexe Produktmischungen durch Sauerstoff/ Methylidin-Austausch, welche teilweise als Radikalrekombinationsprodukte durch GC/MS Analyse und 1 H-NMR-Spektroskopie identifiziert werden konnten. Schema 1. Synthese des Methylidin-Komplexes 1, direkt (oberer Pfeil) oder über das Takai-Olefinierungsreagenz B (unterer Pfeil).
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