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• W1998325520 abstract "Abstract Reactions of the aminocyclopentadienes (C 5 Me 4 H)SiMe 2 NHR (R = Et, allyl, n Pr, t Bu) with [YbI 2 (THF) 2 ] in the presence of two equivalents of potassium 1,2‐diphenylethenide in THF at room temperature gave the diamagnetic half‐sandwich complexes [Yb(η 5 ‐C 5 Me 4 SiMe 2 NHR)L n (μ‐I)] 2 (L = THF, n = 2, L = DME, n = 1). The tert ‐butylamido derivative [Yb(η 5 ‐C 5 Me 4 SiMe 2 NH t Bu)(THF) 2 (μ‐I)] 2 was characterized by X‐ray structural analysis as a dinuclear complex containing a nonchelating aminocyclopentadienyl ligand. Deprotonation of the aminocyclopentadiene (C 5 H 4 t Bu)SiMe 2 NH t Bu with two equivalents of potassium 1,2‐diphenylethenide in THF, followed by reaction with [YbI 2 (THF) 2 ] at 60 °C, gave the trivalent ytterbium ate complex [K(DME)][Yb{(η 5 :η 1 ‐C 5 H 3 t Bu‐3)SiMe 2 N t Bu} 2 ]. A single crystal X‐ray diffraction study of this complex shows polymeric chains consisting of trivalent ytterbocene units with two chelating amidocyclopentadienyl ligands coordinated to potassium ions. Metalation of the aminoindene (C 9 H 7 )SiMe 2 NH t Bu under the same conditions and treatment with [YbI 2 (THF) 2 ] in THF at ambient temperature resulted in the formation of the divalent ytterbocene complex [Yb{η 5 ‐(1‐C 9 H 6 )SiMe 2 NH t Bu} 2 (THF) 2 ]. The reaction of ytterbium naphthalenide [Yb(C 10 H 8 )(THF) 2 ] with one equivalent of (C 9 H 7 )SiMe 2 NH t Bu afforded the bis(indenyl) compound which was isolated as its 2,2′‐bipyridyl adduct [Yb{η 5 ‐(1‐C 9 H 6 )SiMe 2 NH t Bu} 2 (bipy)]. It was shown by single‐crystal structural analysis to exhibit a bent metallocene structure with noncoordinating amino side‐chains. The reaction of (C 5 Me 4 H)CH 2 SiMe 2 NH t Bu, which contains a longer CH 2 SiMe 2 bridge, with [Yb(C 10 H 8 )(THF) 2 ] gave the complex [Li 0.5 ][Yb(μ‐η 5 :η 1 ‐C 5 Me 4 CH 2 SiMe 2 N t Bu)(THF) 2 (μ‐I) 0.5 ]. Single crystal X‐ray structure analysis revealed the presence of polymeric chains consisting of dinuclear iodo‐bridged [Yb(η 5 :η 1 ‐C 5 Me 4 CH 2 SiMe 2 N t Bu)] units with a chelating linked amidocyclopentadienyl ligand, intermolecularly bridged by lithium ions. The lithium ions are bonded in an η 5 ‐manner to both units, forming a lithocene structure. When YbCl 3 was reacted with Li 2 [(C 5 H 3 t Bu‐3)SiMe 2 NCH 2 CH 2 X] (X = NMe 2 , OMe), heterobimetallic complexes Li[Yb{(η 5 :η 1 ‐C 5 H 3 t Bu‐3)SiMe 2 NCH 2 CH 2 X} 2 ] with a helical metallocene structure were isolated. The single crystal structure analysis of one of the three possible diastereomers of Li{Yb[(η 5 :η 1 ‐C 5 H 3 t Bu‐3)SiMe 2 NCH 2 CH 2 NMe 2 ] 2 }, viz. the thermodynamically stable ( R , R )/( S , S ) epimer was performed. When YbCl 3 was reacted with one equivalent of Li 2 [(C 5 H 3 t Bu‐3)SiMe 2 NCH 2 CH 2 NMe 2 ] and reduced “in situ” with one equivalent of sodium 1,2‐diphenylethenide in THF, the ytterbium( II ) metallocene complex [Li(THF)] 2 [Yb{(η 5 ‐C 5 H 3 t Bu‐3)SiMe 2 NH(CH 2 CH 2 NMe 2 )} 2 (μ‐Cl) 2 ] was isolated, which exhibits a structure with the two amino functions coordinating to the lithium ions and the chloro ligands bridging both the lithium and ytterbium centers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)" @default.
• W1998325520 created "2016-06-24" @default.
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• W1998325520 date "2003-02-17" @default.
• W1998325520 modified "2023-10-03" @default.
• W1998325520 title "Di‐ and Trivalent Ytterbium Complexes Containing Linked Amino‐ and Amidocyclopentadienyl Ligands" @default.
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• W1998325520 doi "https://doi.org/10.1002/ejic.200390122" @default.
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