Organoderivatives of Rare Earth Elements

Bochkarev, M. N.; Zakharov, L. N.; Kalinina, G. S.

doi:10.1007/978-94-011-0361-9

Cited by 112 publications

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“…The crystal structure determination revealed 1 to be a centrosymmetric iodo-bridged dimer with trans-disposed aminocyclopentadienyl ligands, similar to the structure adopted by its pentamethylcyclopentadienyl analogue [Yb(η 5 -C 5 Me 5 )- [11] The YbϪO bond lengths fall into the range normally observed for derivatives of divalent ytterbium. [12] Significant differences in the YbϪI and YbϪIЈ bond lengths have been found for 1 [3.0985(5) and 3.3008(5) Å respectively]. The shorter YbϪI distance is similar to the values previously observed for related dimeric Yb II complexes, [10,13] but the YbϪIЈ distance appears to be very long.…”

Section: Resultssupporting

confidence: 83%

Di‐ and Trivalent Ytterbium Complexes Containing Linked Amino‐ and Amidocyclopentadienyl Ligands

2003

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Reactions of the aminocyclopentadienes (C5Me4H)SiMe2NHR (R = Et, allyl, nPr, tBu) with [YbI2(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(η5‐C5Me4SiMe2NHR)Ln(μ‐I)]2 (L = THF, n = 2, L = DME, n = 1). The tert‐butylamido derivative [Yb(η5‐C5Me4SiMe2NHtBu)(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 (C5H4tBu)SiMe2NHtBu with two equivalents of potassium 1,2‐diphenylethenide in THF, followed by reaction with [YbI2(THF)2] at 60 °C, gave the trivalent ytterbium ate complex [K(DME)][Yb{(η5:η1‐C5H3tBu‐3)SiMe2NtBu}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 (C9H7)SiMe2NHtBu under the same conditions and treatment with [YbI2(THF)2] in THF at ambient temperature resulted in the formation of the divalent ytterbocene complex [Yb{η5‐(1‐C9H6)SiMe2NHtBu}2(THF)2]. The reaction of ytterbium naphthalenide [Yb(C10H8)(THF)2] with one equivalent of (C9H7)SiMe2NHtBu afforded the bis(indenyl) compound which was isolated as its 2,2′‐bipyridyl adduct [Yb{η5‐(1‐C9H6)SiMe2NHtBu}2(bipy)]. It was shown by single‐crystal structural analysis to exhibit a bent metallocene structure with noncoordinating amino side‐chains. The reaction of (C5Me4H)CH2SiMe2NHtBu, which contains a longer CH2SiMe2 bridge, with [Yb(C10H8)(THF)2] gave the complex [Li0.5][Yb(μ‐η5:η1‐C5Me4CH2SiMe2NtBu)(THF)2(μ‐I)0.5]. Single crystal X‐ray structure analysis revealed the presence of polymeric chains consisting of dinuclear iodo‐bridged [Yb(η5:η1‐C5Me4CH2SiMe2NtBu)] units with a chelating linked amidocyclopentadienyl ligand, intermolecularly bridged by lithium ions. The lithium ions are bonded in an η5‐manner to both units, forming a lithocene structure. When YbCl3 was reacted with Li2[(C5H3tBu‐3)SiMe2NCH2CH2X] (X = NMe2, OMe), heterobimetallic complexes Li[Yb{(η5:η1‐C5H3tBu‐3)SiMe2NCH2CH2X}2] with a helical metallocene structure were isolated. The single crystal structure analysis of one of the three possible diastereomers of Li{Yb[(η5:η1‐C5H3tBu‐3)SiMe2NCH2CH2NMe2]2}, viz. the thermodynamically stable (R,R)/(S,S) epimer was performed. When YbCl3 was reacted with one equivalent of Li2[(C5H3tBu‐3)SiMe2NCH2CH2NMe2] and reduced “in situ” with one equivalent of sodium 1,2‐diphenylethenide in THF, the ytterbium(II) metallocene complex [Li(THF)]2[Yb{(η5‐C5H3tBu‐3)SiMe2NH(CH2CH2NMe2)}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)

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Section: Resultssupporting

confidence: 83%

Di‐ and Trivalent Ytterbium Complexes Containing Linked Amino‐ and Amidocyclopentadienyl Ligands

2003

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“…The use of charged π-donor ligands and the principle of steric saturation by associated neutral σ-donors or the addition of anionic ligands have dominated organolanthanoid [1] chemistry over the past decades. More recently, however, there has been a growing interest in low-coordinate σ-bonded lanthanoid complexes with bulky substituted organyls, [2,3] Group 14, Group 15, or Group 16 heteroelements.…”

Section: Introductionmentioning

confidence: 99%

σ-Donor versus η6-π-Arene Interactions in Monomeric Europium(II) and Ytterbium(II) Thiolates − An Experimental and Computational Study

Niemeyer

2001

Eur. J. Inorg. Chem.

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Keywords: Ab initio calculations / Lanthanides / π interactions / S ligands / YtterbiumThe base-free, hydrocarbon-soluble complexes M(SAr*) 2 (4a: M = Eu, orange; 4b: M = Yb, purple; Ar* = 2,6-Trip 2 C 6 H 3 ; Trip = 2,4,6-iPr 3 C 6 H 2 ) have been prepared by a protolysis reaction of the Grignard-analogous compound RLnI (R = 2-F 3 CC 6 H 4 ) with HSAr*. Compound 4b has been characterized by melting point, elemental analysis, 1 H, 13 C, and 171 Yb NMR, IR spectroscopy, UV/Vis spectrophotometry, mass spectrometry, and X-ray crystallography. Additionally, the purple Yb III complex YbI 2 (SAr*)(THF) 3 (3) and the yellow DME adduct Yb(SAr*) 2 (dme) 2 (5) have been synthesized and characterized by X-ray crystallography. The solid-state structures of 4a and 4b (as THF or benzene hemisolvates) show monomeric units with the metal atom bonded to two terminal

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“…The structure of 2 is novel as the first authenticated example of an unsubstituted phenoxide bound to a lanthanoid centre. [16,26] There must be a fine balance between formation of a six coordinate µ-OPh (thf-free) species and the observed thf-coordinated structure 2, since OPh is only marginally bulkier than thf. [27] The methoxide and phenoxide groups in 1 and 2 are derived from the ligands L 1 and L 2 , respectively.…”

Section: Resultsmentioning

confidence: 99%

“…[12Ϫ14] These few examples of CϪO cleavage of alkyl ethers contrast the numerous stable coordination complexes of divalent lanthanoids with these ligands. [15,16] In this contribution, we report the unexpected cleavage of the aryl ether CϪO single bond of the anionic bidentate N,O-ligands L 1 , L 2 [L 1 ϭ N(SiMe 3 )C 6 H 4 -2-OMe, L 2 ϭ N(SiMe 3 )C 6 H 4 -2-OPh] by a ytterbium(II) centre and the characterisation of the lanthanoid(III) products [Yb(L 1 ) 2 (µ-OMe)] 2 (1) and [Yb(L 2 ) 2 (OPh)(thf)] (2). The latter is the first structurally authenticated lanthanoid complex with an These are considered to be derived from C−O bond cleavage of the ligand aryl ether moiety by an initially formed Yb II species, e.g.…”

Section: Introductionmentioning

confidence: 99%

Aryl Ether C−O Bond Activation by Organoamidolanthanoid(II) Complexes

Deacon

Forsyth

Scott

2000

Eur. J. Inorg. Chem.

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The reaction of ytterbium metal, HgPh2 and N‐(2‐methoxyphenyl)‐N‐(trimethylsilyl)amine (L1H) or N‐(2‐phenoxyphenyl)‐N‐(trimethylsilyl)amine (L2H) in tetrahydrofuran (thf) unexpectedly yielded the ytterbium(III) complexes [Yb(L1)2(μ‐OMe)]2 (1) and [Yb(L2)2(OPh)(thf)] (2), the structures of which were established by X‐ray crystallography. These are considered to be derived from C−O bond cleavage of the ligand aryl ether moiety by an initially formed YbII species, e.g. the thermally unstable, but crystallographically authenticated [Yb(L1)2(thf)2] (3), which was independently prepared from [Yb{N(SiMe3)2}2(thf)2] and L1H.

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Organoderivatives of Rare Earth Elements

Cited by 112 publications

References 0 publications

Di‐ and Trivalent Ytterbium Complexes Containing Linked Amino‐ and Amidocyclopentadienyl Ligands

Di‐ and Trivalent Ytterbium Complexes Containing Linked Amino‐ and Amidocyclopentadienyl Ligands

σ-Donor versus η6-π-Arene Interactions in Monomeric Europium(II) and Ytterbium(II) Thiolates − An Experimental and Computational Study

Aryl Ether C−O Bond Activation by Organoamidolanthanoid(II) Complexes

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