Die Deprotonierung silylierter Amido-Komplexe von Seltenerdelementen

Karl, Marc; Harms, Klaus; Seybert, Gert; Massa, Werner; Fau, Stefan; Frenking, Gernot; Dehnicke, Kurt

doi:10.1002/(sici)1521-3749(199912)625:12<2055::aid-zaac2055>3.0.co;2-y

Cited by 50 publications

(30 citation statements)

References 7 publications

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“…A straightforward access to a series of alkynyllanthanide amides has been reported by Dehnicke et al 113 The homoleptic tris(silylamides) of cerium, samarium, and europium react with phenylacetylene in THF solution in the presence of NaN(SiMe 3 ) 2 as deprotonating agent according to eq 34 to give the novel bimetallic alkynyllanthanide amides [(Me 3 Si) 2 N] 3 Ln(µ-CtCPh)-Na(THF) 3 .…”

Section: Alkenyl and Alkynyl Complexesmentioning

confidence: 99%

“…A single-crystal X-ray structure determination of the samarium derivative revealed the presence of a bimetallic complex (28) with the phenylacetylide ligand bridging samarium and sodium. 113 Well-defined dimeric µ-ethynyl complexes of yttrium are formed by protolysis of the alkyl derivative [PhC(NSiMe 3 ) 2 ] 2 YCH(SiMe 3 ) 2 or the corresponding hydride with terminal alkynes (R ) H, Me, nPr, tBu, SiMe 3 , Ph) as illustrated in Scheme 12. 77,81 The solid-state structure of [{PhC(NSiMe 3 ) 2 } 2 Y(µ-Ct CH)] 2 with bridging ethynyl ligands has been verified by an X-ray crystal structure analysis.…”

Section: Alkenyl and Alkynyl Complexesmentioning

confidence: 99%

“…Here too hexane-insoluble LiOAr is eliminated besides the protonation product 1,4-bis-(trimethylsilyl)cyclooctatriene. With 36% the yield is[(C 8 H 8 )Ln(µ-Cl)(THF) 2 ] 2 + 2NaOR f [(C 8 H 8 )Ln(µ-OR)(THF)] 2 + 2NaCl R ) Ph, Ln ) Y, Lu R ) 2,6-C 6 H 3 Me 2 , Ln ) Y, Lu R ) (CH 2 ) 3 CHdCH 2 ,Ln ) Dy (63) (COT)Nd(BH 4 )(THF) 2 + NaOEt 98 THF 1/2[(C 8 H 8 )Nd(µ-OEt)(THF)] 2 + NaBH 4 (64) [(C 8 H 8 )Nd(THF) 4 ][BPh 4 ] + NaOEt 98 THF 1/2[(C 8 H 8 )Nd(µ-OEt)(THF)] 2 + NaBPh 4(65) …”

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Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

2002

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Over the years one major challenge has remained in organolanthanide chemistry: the synthesis of homoleptic alkyl and aryl complexes. The simplest organometallic compounds of the rare earths are the species LnR 2 or LnR 3 with the rare earth metals in their common oxidation states Ln 2+ and Ln 3+ which imply the coordination of only two or three ligands to the metal center. This is usually insufficient to meet the lanthanides' demands of steric saturation through high coordination numbers.Hence for a long time, only indirect evidence could be found for the existence of simple homoleptic organolanthanide compounds; the isolation and characterization of compounds belonging to this class were first achieved recently using pentafluorophenyl for Ln 2+ derivatives 12 and very bulky alkyl ligands for Ln 3+ species. [13][14][15] Especially for alkyls, very little structural data are available for compounds without any trimethylsilyl-substituted ligands which generally ensure higher stability. But nevertheless, due to the difficulties of their synthesis and their high reactivity alkyls and aryls still represent an interesting class of compounds. 16 Homoleptic σ-Alkyl ComplexesShortly after the synthesis of the first divalent solvent-free Ln alkyl, [(Me 3 Si) 3 C] 2 Yb, 17 the Eu analogue was prepared similarly by the reaction of EuI 2 and KC(SiMe 3 ) 3 in benzene. 18 It also features the bent structure displayed by the Yb complex but with a slightly smaller C-Eu-C angle (C-Eu-C ) 136°, C-Yb-C ) 137°) and longer Eu-C bonds (Eu-C ) 261 pm, Yb-C ) 249/250 pm). Salt metathesis was then again applied successfully to synthesize the first divalent Sm alkyl, Sm[C(SiMe 3 ) 2 (SiMe 2 OMe)] 2 (THF) Frank T. Edelmann was born in Hamburg, Germany, in 1954. He studied chemistry from 1974 to 1979 at the University of Hamburg, where he obtained his Diplom in 1979 and doctoral degree in 1983. His Ph.D. thesis entitled "The chemistry of the tricarbonyl(fulvene) chromium complexes" was carried out under the supervision of Prof. Ulrich Behrens. This was followed by two years (1983−1985) of postdoctoral research as a Feodor Lynen Fellow of the Alexander-von-Humboldt Foundation in the groups of Professors Josef Takats (

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Section: Alkenyl and Alkynyl Complexesmentioning

confidence: 99%

Section: Alkenyl and Alkynyl Complexesmentioning

confidence: 99%

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Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

2002

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“…They were found to give an insoluble poly(norbornene) in low yield only (a 10%), in toluene or chlorobenzene as a reaction solvent. [89] The Stereochemistry of VinylPoly(norbornene)…”

Section: Chromium and Cobalt Catalystsmentioning

confidence: 99%

The Vinyl Homopolymerization of Norbornene

Janiak¹,

Lassahn

2001

Macromol. Rapid Commun.

210

145

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“…Lithium-2-(tert-butyl-dimethylsilyl)indolid-tris(tetrahydrofuran) liegt (wohl wegen des sperrigen tert-Butylsilyl-substituenten) im Kristall monomer vor [13]. Kalium-2,3-dimethylindolid(DME) 2 [14] ist dimer, Kalium-2,3-dimethylindolid(THF) [14] polymer und Dinatrium-7-methylindolid-hexamethyldisilazid(THF) 2 [15] tetramer aufgebaut. [4].…”

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Strukturen der Alkalimetallsalze aromatischer, heterocyclischer Amide: Synthese und Struktur von Kronenether‐Addukten der Alkalimetall‐indolide

Heldt

Borrmann

Behrens

2003

Zeitschrift anorg allge chemie

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The synthesis of five alkali metal indolide crown ether complexes is reported. Lithium-indolide(12-crown-4) (1) was synthezised from butyllithium, indole, and 12-crown-4; sodium-indolide(15-crown-5) (2) from sodium metal, indole, and 15-crown-5; potassium-indolide(18-crown-6) (3) from potassium hydride, indole, and 18-crown-6. Rubidium-and cesium-indolide(18-crown-6) (4, 5) were made from Rb-and Cs-hexamethyldisilazide, indole, Einleitung 1) Die Alkalimetall-cyclopentadienide, -indenide und -fluorenide sind bekanntlich wichtige Ausgangsverbindungen für die Synthese von Metallocenen der Haupt-und Nebengruppenelemente. Ohne zusätzliche koordinierende Liganden wie Tetrahydrofuran (THF), Dimethoxyethan (DME), Tetramethylethylendiamin (TMEDA) usw. bilden die Alkalimetall-cyclopentadienide polymere Stapelstrukturen aus [1]. Auch Lithium-indenid kristallisiert in Form einer Multidekker-Struktur [2]. Kronenether sind in besonderem Maße fähig, die polymeren Strukturen der basen-freien Alkali-5) wurden aus Rb-bzw. Cs-hexamethyldisilazid, Indol und 18-Krone-6 erhalten. Die Strukturen von 2, 4 und 5 konnten röntgenographisch bestimmt werden. Die Komplexe 2 und 4 sind einkernig, das Indolid-Anion weist eine η 1 (N)-Koordination zum Metallkation auf. Komplex 5 ist zweikernig mit einem zentralen [CsϪNϪ] 2 -Ring.and 18-crown-6. The structures of 2, 4, and 5 could be determined by X-ray diffraction. The complexes 2 and 4 are mononuclear, the indolide anion shows an η 1 (N)-coordination to the metal cation. Complex 5 is dinuclear with a central [CsϪNϪ] 2 -ring.

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Die Deprotonierung silylierter Amido-Komplexe von Seltenerdelementen

Cited by 50 publications

References 7 publications

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

The Vinyl Homopolymerization of Norbornene

Strukturen der Alkalimetallsalze aromatischer, heterocyclischer Amide: Synthese und Struktur von Kronenether‐Addukten der Alkalimetall‐indolide

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