A Monomeric Solvent-Free Bent Lanthanide Dialkyl and a Lanthanide Analog of a Grignard Reagent. Crystal Structures of Yb{C(SiMe3)3}2 and [Yb{C(SiMe3)3}I.cntdot.OEt2]2

Eaborn, Colin; HITCHCOCK, P. B.; Izod, Keith; Smith, J. David

doi:10.1021/ja00105a065

Cited by 162 publications

(105 citation statements)

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“…[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. The IϪYbϪIЈ bond angle in 1 is significantly smaller than that in the C 5 Me 5 analogue.…”

Section: Resultssupporting

confidence: 78%

“…These compounds are diamagnetic, corresponding to the Yb II oxidation state; 1 H, 13 C NMR and IR spectra show the presence of the aminocyclopentadiene ligands in deprotonated form. However microanalysis failed to give reproducible data and all attempts to obtain samples suitable for X-ray crystal structure analysis failed.…”

Section: Resultsmentioning

confidence: 99%

“…The compound crystallizes in a polymeric chain structure; crystal and structure refinement data are compiled in Table 2. Complex 8 exhibits the unusual [13] Recently we have shown that reactions of yttrium and lutetium chlorides with dilithium derivatives of tridentate amidocyclopentadienyl ligands result in the formation of chiral lanthanocene complexes with a unique heterobimetallic core. [25] Ytterbium trichloride reacted with Li 2 [(C 5 H 3 tBu-3)SiMe 2 NCH 2 CH 2 X] (X ϭ NMe 2 , OMe) in THF or DME regardless of the reagent ratio, solvent, and the isolation method, to give heterobimetallic complexes Li[Yb{η 5 :η 1 -C 5 H 3 tBu-3)SiMe 2 NCH 2 CH 2 X} 2 ] (X ϭ NMe 2 , 9; OMe, 10) with a helical metallocene structure (Scheme 6).…”

Section: Resultsmentioning

confidence: 99%

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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: 78%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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

2003

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“…Only af ew complexes have been prepared and structurally characterised. Dimeric [Yb{C(SiMe 3 ) 2 (SiMe 2 X)}I(OEt 2 )] 2 (X = CH= CH 2 ,O Me, Me) compounds, reported by Smith and co-workers, were prepared by the addition of C(SiMe 3 ) 2 (SiMe 2 X)I to ytterbium metal in diethyl ether [12,13] and, notably, monomeric cis-[Yb(C 6 H 3 Ph 2 -2,6)I(thf) 3 ]w as isolated. [14] The chemistry of "RLnX" is complicated by oxidationt oL n III for Ln = Sm, Eu, and Yb, and the existence of Schlenke quilibria in both oxidation states.…”

Section: Introductionmentioning

confidence: 99%

Lanthanoid Pseudo‐Grignard Reagents: A Major Untapped Resource

Ali

Deacon

Junk

et al. 2017

Chemistry A European J

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Pseudo-Grignardr eagents PhLnI (Ln = Yb, Eu), readily prepared by the oxidative addition of iodobenzene to ytterbium or europium metal at À78 8Cint etrahydrofuran (THF) or 1,2-dimethoxyethane (DME), react with ar ange of bulky N,N'-bis(aryl)formamidines to generate an extensive series of Ln II or more rarely Ln III complexes,n amely [Eu(Dipp-, and [Yb(XylForm) 2 I(dme)]·dme (7b){ (Form = ArNCHNAr;X ylForm (Ar = 2,6-Me 2 C 6 H 3 ), MesForm (Ar = 2,4,6-Me 3 C 6 H 2 ), DippForm (Ar = 2,6-iPr 2 C 6 H 3 )}. Reaction of PhEuI and MesFormH in DME consistently gave 2, and reactionw ith XylFormH in THF gave 4.E uropium complexes 1 and 3a are seven-coordinate divalent monomers, whilst 3b is as even-coordinate dme-bridged polymer.C omplex 5a of the smaller Yb II is as ix-coordinate monomer,b ut the related 6 and 7a are six-coordinatei odide-bridged dimers. 4 is at rivalent seven-coordinate hydroxide-bridged dimer,w hereas complexes 5b and 7b are seven-coordinate monomeric Yb III derivatives. Ac haracteristic structural feature is that iodide ligands are cisoid to the formamidinate ligand.T oi llustrate the synthetic scope of the pseudoGrignardr eagents,[ Yb(Ph 2 pz)I(thf) 4 ]( Ph 2 pz = 3,5-diphenylpyrazolate) was oxidised with 1,2-diiodoethane to afford seven-coordinate monomeric pyrazolato-ytterbium (III)

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“…Use of stabilizing silyl-groups in the bulky bis-and tristrimethylsilyl ligands [ϪCH(SiMe 3 ) 2 and ϪC(SiMe 3 ) 3 ] made it first possible to obtain solid state structures of neutral homoleptic lanthanide alkyls [4,5,6]. Especially the former ligand has been widely used and intensively studied in organolanthanide chemistry [7].…”

Section: Introductionmentioning

confidence: 99%

Organometallic Compounds of the Lanthanides. 157 [1] The Molecular Structure of Tris(trimethylsilylmethyl)samarium, -erbium, -ytterbium, and -lutetium

Schumann

Freckmann

Dechert

2002

Z. anorg. allg. Chem.

116

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SmCl 3 reacts with Me 3 SiCH 2 Li in THF yielding Sm(CH 2 SiMe 3 ) 3 (THF) 3 (1). The single crystal X-ray structural analyses of 1, Er(CH 2 SiMe 3 ) 3 (THF) 2 (2), Yb(CH 2 SiMe 3 ) 3 (THF) 2 (3), and Lu(CH 2 SiMe 3 ) 3 (THF) 2 (4) show the Sm atom in a facoctahedral coordination and the heavier lanthanides Er, Yb, and Metallorganische Verbindungen der Lanthanoide. 157 [1] Die Molekülstruktur von Tris(trimethylsilylmethyl)samarium, -erbium, -ytterbium und -lutetium

show abstract

A Monomeric Solvent-Free Bent Lanthanide Dialkyl and a Lanthanide Analog of a Grignard Reagent. Crystal Structures of Yb{C(SiMe3)3}2 and [Yb{C(SiMe3)3}I.cntdot.OEt2]2

Cited by 162 publications

References 1 publication

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

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

Lanthanoid Pseudo‐Grignard Reagents: A Major Untapped Resource

Organometallic Compounds of the Lanthanides. 157 [1] The Molecular Structure of Tris(trimethylsilylmethyl)samarium, -erbium, -ytterbium, and -lutetium

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