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• W4236760922 abstract "The reaction of YbCl3 with two equivalents of NaN-(SiMe3)2 has afforded a mixture of several ytterbium bis(trimethylsilyl) amides with the known complexes [Yb{N(SiMe3)2}2(μ-Cl)(thf)]2 (1) and [Yb{N(SiMe3)2}3](4) as the main products and the cluster compound [Yb3Cl4O{N(SiMe3)2}3(thf)3](2) as a minor product. Treatment of 1 and 2 with hot n-heptane gave the basefree complex [Yb{N(SiMe3)2}2(μ-Cl)]2 (3) in small yield. The structures of compounds 1—4 and the related peroxo complex [Yb2{N(SiMe3)2}4(μ-O2)(thf)2](5) have been investigated by single crystal X-ray diffraction. In the solid-state, 3 shows chlorobridged dimers with terminal amido ligands (av. Yb—Cl = 262.3 pm, av. Yb—N = 214.4 pm). Additional agostic interactions are observed from the ytterbium atoms to four methyl carbon atoms of the bis(trimethylsilyl)amido groups (Yb···C = 284—320 pm). DFT calculations have been performed on suitable model systems ([Yb2(NH2)4(μ-Cl)2(OMe2)2](1m), [Yb2(NH2)4(μ-Cl)2](3m), [Yb-(NH2)3](4m), [Yb2(NH24(μ-O2)(OMe2)2](5m), [Yb{N-(SiMe3)2}2Cl] (3m/2) and Ln(NH2)2NHSiMe3 (Ln = Yb (6m), Y (7m)) in order to rationalize the different experimentally observed Yb—N distances, to support the assignment of the O—O stretching vibration (775 cm -1) in the Raman spectrum of complex 5 and to examine the nature of the agostic-type interactions in σ-donorfree 3. Synthese und strukturelle Charakterisierung verschiedener Ytterbiumbis(trimethylsilyl)amide darunter σ-donorfreies [Yb{N(SiMe3)2}2(μ-Cl)]2 — Ein koordinativ ungesättigter Komplex mit zusätzlichen agostischen Yb···(H3C-Si) Wechselwirkungen Durch Reaktion von YbCl3 mit zwei Äquivalenten NaN(SiMe3)2 wurde eine Mischung verschiedener Ytterbium-bis(trimethylsilyl)amide, mit den bekannten Komplexen [Yb{N(SiMe3)2}2(μ-Cl)(thf)]2 (1) und [Yb{N(SiMe3)2}3](4) als Hauptprodukte und der Clusterverbindung [Yb3Cl4O-{N(SiMe3)2}3(thf)3](2) als Nebenprodukt, erhalten. Die Behandlung von 1 und 2 mit heißem n-Heptan führte in geringer Ausbeute zur Bildung des basenfreien Komplexes [Yb{N(SiMe3)2}2(μ-Cl)]2 (3). Die Strukturen der Verbindungen 1—4 und des verwandten Peroxo-Komplexes [Yb2{N(SiMe3)2}4(μ-O2)(thf)2](5) wurden mittels Röntgenbeugung an Einkristallen untersucht. In der Festkörperstruktur von 3 liegen chloridverbrückte Dimere mit terminalen Amidliganden vor (Mittelwerte Yb—Cl = 262, 3 pm, Yb—N = 214, 4 pm). Zusätzliche agostische Wechselwirkungen werden von den Ytterbiumatomen zu vier Methylkohlenstoffatomen der Bis-(trimethylsilyl)amid-Gruppen beobachtet (Yb···C = 284—320 pm). DFT Rechnungen an geeigneten Modellsystemen ([Yb2(NH2)4-(μ-Cl)2(OMe2)2](1m), [Yb2(NH2)4(μ-Cl)2](3m), [Yb(NH2)3](4m), [Yb2(NH2)4(μ-O2)(OMe2)2](5m), [Yb{N(SiMe3)2}2Cl] (3m/2) und Ln(NH2)2NHSiMe3 (Ln = Yb (6m), Y (7m)) wurden durchgeführt, um die unterschiedlichen experimentell bestimmten Yb—N-Abstände zu verstehen, die Zuordnung der O—O-Streckschwingung (775 cm -1) im Ramanspektrum des Komplexes 5 zu ermöglichen und die Natur der agostischen Wechselwirkungen in σ-donorfreiem 3 zu untersuchen." @default.
• W4236760922 created "2022-05-12" @default.
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• W4236760922 date "2002-03-01" @default.
• W4236760922 modified "2023-10-14" @default.
• W4236760922 doi "https://doi.org/10.1002/1521-3749(200203)628:3<647::aid-zaac647>3.3.co;2-c" @default.
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