Tieftemperatur‐Oxidation in flüssigem Ammoniak: [Eu2(Ind)4(NH3)6], das erste Indolat eines Selten‐Erd‐Elementes

Müller‐Buschbaum, Klaus

doi:10.1002/zaac.200400038

Cited by 37 publications

(11 citation statements)

References 33 publications

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“…To our knowledge, these complexes represent the first example of the rare-earth metal alkyl complexes bearing a m-h 2 :h 1 -coordinated indolyl ligand. [26] The angles of N1'-Y1-C18 114.47 (17)8, N2-Y1-C18 113.37(17)8, N2-Y1-N1'131.96 (14)8, N2-Y1-O1 95.60 (15)8, O1-Y1-C18 94.45 (19)8, N1'-Y1-C3 86.99 (14)8 in 1 show that the coordination geometry of the central metal can be described as a distorted triangular bipyramid. The differences of REÀN2 bond lengths of 2.182(4) in 1, 2.182(3) in 2, 2.147(3) in 3, and the REÀN1' bond lengths of 2.366(4) in 1, and 2.369(3) in 2 and 2.303(3) in 3 can be mainly attributed to the ionic radii difference of the central metal.…”

Section: Resultsmentioning

confidence: 99%

Dinuclear Rare‐Earth Metal Alkyl Complexes Supported by Indolyl Ligands in μ‐η²:η¹:η¹ Hapticities and their High Catalytic Activity for Isoprene 1,4‐cis‐Polymerization

Zhang

Wei

Guo

et al. 2014

Chemistry A European J

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Two series of new dinuclear rare-earth metal alkyl complexes supported by indolyl ligands in novel μ-η(2) :η(1) :η(1) hapticities are synthesized and characterized. Treatment of [RE(CH2 SiMe3 )3 (thf)2 ] with 1 equivalent of 3-(tBuN=CH)C8 H5 NH (L1 ) in THF gives the dinuclear rare-earth metal alkyl complexes trans-[(μ-η(2) :η(1) :η(1) -3-{tBuNCH(CH2 SiMe3 )}Ind)RE(thf)(CH2 SiMe3 )]2 (Ind=indolyl, RE=Y, Dy, or Yb) in good yields. In the process, the indole unit of L1 is deprotonated by the metal alkyl species and the imino C=N group is transferred to the amido group by alkyl CH2 SiMe3 insertion, affording a new dianionic ligand that bridges two metal alkyl units in μ-η(2) :η(1) :η(1) bonding modes, forming the dinuclear rare-earth metal alkyl complexes. When L1 is reduced to 3-(tBuNHCH2 )C8 H5 NH (L2 ), the reaction of [Yb(CH2 SiMe3 )3 (thf)2 ] with 1 equivalent of L2 in THF, interestingly, generated the trans-[(μ-η(2) :η(1) :η(1) -3-{tBuNCH2 }Ind)Yb(thf)(CH2 SiMe3 )]2 (major) and cis-[(μ-η(2) :η(1) :η(1) -3-{tBuNCH2 }Ind)Yb(thf)(CH2 SiMe3 )]2 (minor) complexes. The catalytic activities of these dinuclear rare-earth metal alkyl complexes for isoprene polymerization were investigated; the yttrium and dysprosium complexes exhibited high catalytic activities and high regio- and stereoselectivities for isoprene 1,4-cis-polymerization.

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Section: Resultsmentioning

confidence: 99%

Dinuclear Rare‐Earth Metal Alkyl Complexes Supported by Indolyl Ligands in μ‐η²:η¹:η¹ Hapticities and their High Catalytic Activity for Isoprene 1,4‐cis‐Polymerization

Zhang

Wei

Guo

et al. 2014

Chemistry A European J

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“…These complexes were fully characterized by IR, elemental analysis, and single-crystal X-ray diffraction. The complexes 2a, 2b, and 6 were additionally characterized by 1 H NMR and 13 C NMR spectroscopic study.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The 1 H NMR spectrum of complex 2a showed the disappearance of the characteristic sharp imine resonance of NCH at 8.63 ppm, 26 and instead the appearance of the doublet proton resonances of NCHCH 2 at 4.94 ppm (d, J = 11.7 Hz), which is similar to the proton resonances at 5.0 ppm of an amine group formed by an alkyl insertion to the imine group in our previous works. 17a The corresponding 13 C NMR spectrum showed a resonance at 51.3 ppm. Thus, the 1 H (or 13 C) NMR spectra for complex 2a further confirmed the formation of the new C−C bond.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Reactivity of 3-Imino-Functionalized Indoles with Rare-Earth-Metal Amides: Unexpected Substituent Effects on C–H Activation Pathways and Assembly of Rare-Earth-Metal Complexes

Zhu

Wei

et al. 2016

Organometallics

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The reactivities of different 3-imino-functionalized indoles with rare-earth-metal amides [(Me 3 Si) 2 N] 3 RE(μ-Cl)Li(THF) 3 were studied to reveal unexpected substituent effects on C−H bond activation pathways, leading to the formation of unusual rare-earth-metal complexes. The reactions of 3-(tert-butylimino)indole with [(Me 3 Si) 2 N] 3 RE(μ-Cl)Li(THF) 3 produced tetranuclear rare-earth-metal complexes {[η 1 :(μ 2 -η 1 :η 1 ):η 1 -3-(tBuNCH)C 8 H 4 N]RE 2 (μ 2 -Cl) 2 (THF)[N(SiMe 3 ) 2 ]-(η 1 :η 1 -[μ-η 5 :η 2 -3-(tBuNCH)C 8 H 5 N] 2 Li)} 2 (RE = Ho (1a), Er (1b)), incorporating a unique indolyl-1,2-dianion through sp 2 C−H activation bonded with the central metal in η 1 :(μ 2 -η 1 :η 1 ) mode. The reactions of 3-(phenylimino)indole with [(Me 3 Si) 2 N] 3 RE(μ-Cl)Li(THF) 3 afforded novel binuclear complexes formulated as {3-[PhNCH(CH 2 SiMe 2 )N(SiMe 3 )]-C 8 H 5 NRE(THF)(μ 2 -Cl)Li(THF) 2 } 2 (RE = Y (2a), Sm (2b), Dy (2c), Yb (2d)) through an unexpected sp 3 C−H bond activation with subsequent C−C bond coupling reactions. Treatment of 3-(2-methylphenylimino)indole or 3-(4methylphenylimino)indole with [(Me 3 Si) 2 N] 3 Yb(μ-Cl)Li(THF) 3 generated the corresponding dinuclear rare-earth-metal amido complexes {3-[(2-MePh)NCH(CH 2 SiMe 2 )N(SiMe 3 )]C 8 H 5 NYb(THF)(μ 2 -Cl)Li(THF) 2 } 2 (3) and {3-[(4-MePh)NCH-(CH 2 SiMe 2 )N(SiMe 3 )]C 8 H 5 NYb(THF)(μ 2 -Cl)Li(THF) 2 } 2 (4), following the same pathway for the formation of complexes 2a−d. Treatment of 3-(4-tert-butylphenylimino)indole with [(Me 3 Si) 2 N] 3 RE(μ-Cl)Li(THF) 3 afforded new hexanuclear rareearth-metal complexes {3-[(4-t Bu-Ph)NHCH(CH 2 SiMe 2 )N(SiMe 3 )]C 8 H 5 NREN(SiMe 3 ) 2 } 6 (RE = Dy (5a), Ho (5b), Er (5c)) via sp 3 C−H bond activation followed by C−C bond coupling reactions. In contrast, under the same conditions as those for the preparation of 5, the reaction with the corresponding yttrium complex provided the new heterohexayttrium complex {3-[(4-tBu-Ph)NCH(CH 2 SiMe 2 )N(SiMe 3 )]C 8 H 5 NYN(SiMe 3 ) 2 Li(THF)} 6 ( 6), having a 4-tBu-anilido moiety. All of these complexes were fully characterized by elemental analysis, spectroscopic methods, and X-ray structure analysis. Plausible pathways for the formation of these different rare-earth-metal complexes were proposed.

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“…[8] Because of the formation of an electride solution, these metals can be oxidized by amines at À50 8C. [9] Thus, the solvent-free melt and solvothermal syntheses that are employed for the preparation of homoleptic amides of rareearth elements [10] [Eq.…”

mentioning

confidence: 99%

[Yb₃N(dpa)₆][Yb(dpa)₃]: A Molecular Nitride of a Rare‐Earth Metal with a Yb₃N Unit

Quitmann

Müller‐Buschbaum

2004

Angew Chem Int Ed

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Centered by a nitride ion: The oxidation of ytterbium with 2,2′‐dipyridylamine in liquid ammonia at low temperatures leads to the novel compound [Yb3N(dpa)6][Yb(dpa)3], which is unique among homoleptic dipyridylamides of the rare‐earth metals. The complete deprotonation of NH3 provides the first molecular nitride of a rare‐earth metal with a Yb3N unit (see picture; C blue, N green, Yb silver).

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Tieftemperatur‐Oxidation in flüssigem Ammoniak: [Eu₂(Ind)₄(NH₃)₆], das erste Indolat eines Selten‐Erd‐Elementes

Cited by 37 publications

References 33 publications

Dinuclear Rare‐Earth Metal Alkyl Complexes Supported by Indolyl Ligands in μ‐η²:η¹:η¹ Hapticities and their High Catalytic Activity for Isoprene 1,4‐cis‐Polymerization

Dinuclear Rare‐Earth Metal Alkyl Complexes Supported by Indolyl Ligands in μ‐η²:η¹:η¹ Hapticities and their High Catalytic Activity for Isoprene 1,4‐cis‐Polymerization

Reactivity of 3-Imino-Functionalized Indoles with Rare-Earth-Metal Amides: Unexpected Substituent Effects on C–H Activation Pathways and Assembly of Rare-Earth-Metal Complexes

[Yb₃N(dpa)₆][Yb(dpa)₃]: A Molecular Nitride of a Rare‐Earth Metal with a Yb₃N Unit

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Tieftemperatur‐Oxidation in flüssigem Ammoniak: [Eu2(Ind)4(NH3)6], das erste Indolat eines Selten‐Erd‐Elementes

Cited by 37 publications

References 33 publications

Dinuclear Rare‐Earth Metal Alkyl Complexes Supported by Indolyl Ligands in μ‐η2:η1:η1 Hapticities and their High Catalytic Activity for Isoprene 1,4‐cis‐Polymerization

Dinuclear Rare‐Earth Metal Alkyl Complexes Supported by Indolyl Ligands in μ‐η2:η1:η1 Hapticities and their High Catalytic Activity for Isoprene 1,4‐cis‐Polymerization

Reactivity of 3-Imino-Functionalized Indoles with Rare-Earth-Metal Amides: Unexpected Substituent Effects on C–H Activation Pathways and Assembly of Rare-Earth-Metal Complexes

[Yb3N(dpa)6][Yb(dpa)3]: A Molecular Nitride of a Rare‐Earth Metal with a Yb3N Unit

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Tieftemperatur‐Oxidation in flüssigem Ammoniak: [Eu₂(Ind)₄(NH₃)₆], das erste Indolat eines Selten‐Erd‐Elementes

Dinuclear Rare‐Earth Metal Alkyl Complexes Supported by Indolyl Ligands in μ‐η²:η¹:η¹ Hapticities and their High Catalytic Activity for Isoprene 1,4‐cis‐Polymerization

Dinuclear Rare‐Earth Metal Alkyl Complexes Supported by Indolyl Ligands in μ‐η²:η¹:η¹ Hapticities and their High Catalytic Activity for Isoprene 1,4‐cis‐Polymerization

[Yb₃N(dpa)₆][Yb(dpa)₃]: A Molecular Nitride of a Rare‐Earth Metal with a Yb₃N Unit