Preparation of Anhydrous Lanthanon Halides.

Taylor, Moddie D.

doi:10.1021/cr60220a001

Cited by 119 publications

(47 citation statements)

References 44 publications

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“…analyses were performed on aP erkinElmer 2400 Series II CHNS elemental analyzer.U V/Vis spectra were collected in THF at 298 K using aV arian Cary 50 Scan UV/Vis spectrophotometer.P otassium and rubidium metal (Aldrich) were used as received. Anhydrous LnCl 3 (Ln = Nd, Gd, Tb, Dy,H o, Er,T m), [39] and Ln(NR 2 ) 3 (R = SiMe 3 ) [21] were prepared according to literature procedures. 2.2.2-Cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, Aldrich) was placed under vacuum (10 À4 torr) for 12 hbefore use.…”

Section: Methodsmentioning

confidence: 99%

Synthesis, Structure, and Magnetism of Tris(amide) [Ln{N(SiMe₃)₂}₃]¹⁻ Complexes of the Non‐traditional +2 Lanthanide Ions

Ryan

Darago

Balasubramani

et al. 2018

Chemistry A European J

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A new series of Ln complexes has been synthesized that overturns two previous generalizations in rare-earth metal reduction chemistry: that amide ligands do not form isolable complexes of the highly reducing non-traditional Ln ions, and that yttrium is a good model for the late lanthanides in these reductive reactions. Reduction of Ln(NR ) (R=SiMe ) complexes in THF under Ar with M=K or Rb in the presence of 2.2.2-cryptand (crypt) forms crystallographically characterizable [M(crypt)][Ln(NR ) ] complexes not only for the traditional Tm ion and the configurational crossover ions, Nd and Dy , but also for the non-traditional Gd , Tb , Ho , and Er ions. Crystallographic data as well as UV/Vis, magnetic susceptibility, and density functional theory studies are consistent with the accessibility of 4f 5d configurations for Ln ions in this tris(silylamide) ligand environment. The Dy complex, [K(crypt)][Dy(NR ) ], has a higher magnetic moment than previously observed for any monometallic complex: 11.67 μ .

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Section: Methodsmentioning

confidence: 99%

Synthesis, Structure, and Magnetism of Tris(amide) [Ln{N(SiMe₃)₂}₃]¹⁻ Complexes of the Non‐traditional +2 Lanthanide Ions

Ryan

Darago

Balasubramani

et al. 2018

Chemistry A European J

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“…NMR solvents (Cambridge Isotope Laboratories) were dried over NaK/benzophenone, degassed by three freeze−pump−thaw cycles, and vacuum transferred prior to use. Anhydrous LnCl 3 (Ln = Y, La, Ce, Dy), 20 KCp′ (Cp′ = C 5 H 4 SiMe 3 ), 21 KC 8 , 22 Cp′ 3 Ln (Ln = Y, 2 La, 21 Reaction of 1-Ce with Naphthalene. In a glovebox, a solution of naphthalene (6 mg, 0.05 mmol) in THF (1 mL) was added to a stirred dark purple solution of [K(2.2.2-cryptand)][Cp′ 3 Ce]·THF, 1-Ce (90 mg, 0.087 mmol), in THF (2 mL).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Reactivity of the Ln²⁺ Complexes [K(2.2.2-cryptand)][(C₅H₄SiMe₃)₃Ln]: Reduction of Naphthalene and Biphenyl

2015

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The reductive capacity of the recently discovered Ln 2+ complexes [K(2.2.2-cryptand)][Cp′ 3 Ln], 1-Ln (Cp′ = C 5 H 4 SiMe 3 ; Ln = Y, La, Ce, Dy), has been probed by examining their reactions with aromatic hydrocarbons. [K-(2.2.2-cryptand)][Cp′ 3 Y], 1-Y, is capable of reducing naphthalene and forms a mixture of the naphthalenide dianion complex [K(2.2.2-cryptand)][Cp′ 2 Y(η 4 -C 10 H 8 )], 2-Y, as well as the ligand redistribution product [K(2.2.2-cryptand)][Cp′ 4 Y], 3-Y, and the cyclopentadienyl ligand salt [K(2.2.2-cryptand)]-[Cp′], 4. Naphthalene is reduced analogously by 1-La, 1-Ce, and 1-Dy. Each complex in the yttrium reaction was synthesized independently to confirm its identity in the mixture. Complex 2-Y was prepared from [Cp′ 2 Y(THF) 2 ]-[BPh 4 ], 5 (synthesized from [Et 3 NH][BPh 4 ] and Cp′ 3 Y), and K/naphthalene. Complex 3-Y was obtained by adding KCp′ to Cp′ 3 Y in the presence of 2.2.2-cryptand. [K(2.2.2-cryptand)][Cp′] was synthesized from 2.2.2-cryptand and KCp′. Each C 10 unit in the reduced naphthalene products, 2-Y, 2-La, 2-Ce, and 2-Dy, is bent with four carbon atoms of one ring oriented toward the metal, while the remaining six carbon atoms form a planar ring consistent with (η 4 -C 10 H 8 ) 2− coordination. In the solid state, 3-Y contains one η 1 -Cp′ ligand and three η 5 -Cp′ rings, whereas all four Cp′ rings in 3-La have η 5 -coordination. In the solid-state structure of 4, the (Cp′) − anion is not coordinated to potassium, which is encapsulated by the cryptand and located 7.063 Å from the ring centroid. Complex 1-Y also reduces biphenyl to form [K(2.2.2-cryptand)][Cp′ 2 Y(η 6 -C 6 H 5 Ph)], 6-Y, which contains a dianion with a planar aromatic phenyl ring as a substituent on a nonplanar η 6 -C 6 ring oriented toward the metal ion. ■ INTRODUCTIONRecently, the number of +2 ions available in the lanthanide series in soluble molecular complexes has been expanded from the traditional list of six, namely, Eu 2+ , Yb 2+ , Sm 2+ , Tm 2+ , Dy 2+ , and Nd 2+ , to the rest of the lanthanides except radioactive promethium via the potassium graphite reactions shown in Schemes 1 1 and 2. 2−4 The availability of these complexes allows the reaction chemistry of these new oxidation states to be investigated for the first time.A traditional way to characterize reducing agents too reactive for reproducible electrochemistry is to treat them with polycyclic hydrocarbons of known reduction potential. 5−8 This was initially used to characterize the reactivity 5 of (C 5 Me 5 ) 2 Sm 9 and subsequently used for NdI 2 6 and DyI 2 . 7 (C 5 Me 5 ) 2 Sm can reduce anthracene (−1.98 V vs SCE 10 ) to form [(C 5 Me 5 ) 2 Sm] 2 (μ-C 14 H 10 ), but it does not reduce naphthalene (−2.60 V vs SCE 10 ). 5 The stronger reductants, NdI 2 and DyI 2 , reduce naphthalene in 1,2-dimethoxyethane (DME) and THF to produce [NdI 2 (THF) 3 ] 2 (μ-C 10 H 8 ) 6 and (C 10 H 8 )DyI(DME) 2 , 7 respectively. Although other reduced naphthalene complexes of the rare earth ions are known, 8,11−18 their preparations involve either (a) initial...

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“…Ln(III) halogenides, the raw material of organolanthanide, is another class of well explored ROP initiators for lactones. They are generally prepared by dehydration of LnCl 3 N (H 2 O) x (x = 6,7) using NH 4 Cl (Scheme 3) [46][47][48] . An analogous route prepares LnBr 3 .…”

Section: Synthesis Of Rare Earth Complexesmentioning

confidence: 99%

Rare earth metal initiated ring-opening polymerization of lactones

Agarwal¹,

Mast

Dehnicke

et al. 2000

Macromol. Rapid Commun.

122

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Preparation of Anhydrous Lanthanon Halides.

Cited by 119 publications

References 44 publications

Synthesis, Structure, and Magnetism of Tris(amide) [Ln{N(SiMe₃)₂}₃]¹⁻ Complexes of the Non‐traditional +2 Lanthanide Ions

Synthesis, Structure, and Magnetism of Tris(amide) [Ln{N(SiMe₃)₂}₃]¹⁻ Complexes of the Non‐traditional +2 Lanthanide Ions

Reactivity of the Ln²⁺ Complexes [K(2.2.2-cryptand)][(C₅H₄SiMe₃)₃Ln]: Reduction of Naphthalene and Biphenyl

Rare earth metal initiated ring-opening polymerization of lactones

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Preparation of Anhydrous Lanthanon Halides.

Cited by 119 publications

References 44 publications

Synthesis, Structure, and Magnetism of Tris(amide) [Ln{N(SiMe3)2}3]1− Complexes of the Non‐traditional +2 Lanthanide Ions

Synthesis, Structure, and Magnetism of Tris(amide) [Ln{N(SiMe3)2}3]1− Complexes of the Non‐traditional +2 Lanthanide Ions

Reactivity of the Ln2+ Complexes [K(2.2.2-cryptand)][(C5H4SiMe3)3Ln]: Reduction of Naphthalene and Biphenyl

Rare earth metal initiated ring-opening polymerization of lactones

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Synthesis, Structure, and Magnetism of Tris(amide) [Ln{N(SiMe₃)₂}₃]¹⁻ Complexes of the Non‐traditional +2 Lanthanide Ions

Synthesis, Structure, and Magnetism of Tris(amide) [Ln{N(SiMe₃)₂}₃]¹⁻ Complexes of the Non‐traditional +2 Lanthanide Ions

Reactivity of the Ln²⁺ Complexes [K(2.2.2-cryptand)][(C₅H₄SiMe₃)₃Ln]: Reduction of Naphthalene and Biphenyl