Herstellung von Tetrahydrofuranverbindungen der Seltenerdchloride

Rossmanith, K.; Auer-Welsbach, C.

doi:10.1007/bf00909477

Cited by 24 publications

(25 citation statements)

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“…3 features a four-co-ordinated scandium centre with a distorted tetrahedral arrangement of the ligands. A similar geometry has recently been observed in [Y{N(SiHMe 2 ) 2 } 3 -(carbene)] 13 (Table 1) …”

Section: Structural Chemistry Of [Ln{n(sihme 2 ) 2 } 3 (Thf) X ]supporting

confidence: 66%

Synthesis and structural characterisation of rare-earth bis(dimethylsilyl)amides and their surface organometallic chemistry on mesoporous MCM-41 †

Anwander

Runte

Eppinger

et al. 1998

J. Chem. Soc., Dalton Trans.

261

227

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Rare-earth silylamides of type [Ln{N(SiHMe 2 ) 2 } 3 (thf) x ] (Ln = Sc, Y, La, Nd, Er or Lu) have been prepared in high yield by reaction of 2.9 equivalents of Li[N(SiHMe 2 ) 2 ] with [LnCl 3 (thf) x ] in n-hexane or thf, depending on the solubility of the rare-earth halide precursor. The complexes [Ln{N(SiHMe 2 ) 2 } 3 (thf) 2 ] (Ln = Y, La to Lu) are isostructural in the solid state, adopting the preferred (3 ϩ 2, distorted) trigonal bipyramidal geometry, whilst [Sc{N(SiHMe 2 ) 2 } 3 (thf)] has a distorted tetrahedral co-ordination geometry and short Sc ؒ ؒ ؒ Si contacts in the solid state. The reaction of [Y{N(SiHMe 2 ) 2 } 3 (thf) 2 ] with varying amounts of AlMe 3 resulted in desolvation and alkylation with formation of AlMe 3 (thf), {AlMe 2 [µ-N(SiHMe 2 ] 2 } 2 and heterobimetallic (Y/Al) species. The generation of surface-bonded '(᎐ ᎐ ᎐ SiO) x Y[N(SiHMe 2 ) 2 ] y ' and '᎐ ᎐ ᎐ SiOSiHMe 2 ' moieties via the grafting of [Y{N(SiHMe 2 ) 2 } 3 (thf) 2 ] onto the mesoporous silicate MCM-41 is described in detail. Consideration is given to the factors governing the siloxide formation and silylation reactions, and the thermal stability of the surface species.Rare-earth amides, and in particular silylamides, 1 are of potential relevance in catalysis 2 and the material sciences. 3 Furthermore, the synthetic versatility of the Ln᎐N(SiMe 3 ) 2 moiety is well established in amine elimination reactions known as the silylamide route (Scheme 1). 1,4 Rare-earth amides are also capable of alkylation reactions via Lewis acid-base derived heterobimetallic species. 5,6 Advantages of the Ln᎐N(SiMe 3 ) 2 -based silylamide route are (i) facile availability of mono-and heterobi-metallic amide precursors, (ii) favourable (mild) reaction conditions including non-co-ordinating solvents, ambient temperature, smooth work-up procedures and 'quantitative' yield, (iii) avoidance of halide contamination and (iv) donor ligand-free products due to the weak donor capability of the released silylamine. 1 Complexes [Ln{N(SiHMe 2 ) 2 } 3 (thf) 2 ] derived from the sterically less bulky bis(dimethylsilyl)-amide ligand were introduced better to cope with the steric requirements of catalytically relevant, bulky and chelating ancillary ligands such as salen or linked cyclopentadienyl derivatives. 7 We report here a detailed synthetic and structural examination of these versatile synthetic building blocks. In addition, AlMe 3 -directed desolvation and alkylation reactions are discussed.Very recently, we found that many features of the homogeneously performed silylamide route can be transferred to a heterogeneous medium (Scheme 1). 8 Such a supramolecular approach allowed the grafting of rare-earth silylamide complexes onto a mesoporous aluminosilicate of type MCM-41 9,10 via surface organometallic chemistry. 11 The presence of 'Si᎐H' as a spectroscopic probe helped to unravel the chemical anchoring of the silylamides which proceeds via siloxide formation and silylation reactions. In this work more light will be shed on the surface organometallic chem...

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Section: Structural Chemistry Of [Ln{n(sihme 2 ) 2 } 3 (Thf) X ]supporting

confidence: 66%

Synthesis and structural characterisation of rare-earth bis(dimethylsilyl)amides and their surface organometallic chemistry on mesoporous MCM-41 †

Anwander

Runte

Eppinger

et al. 1998

J. Chem. Soc., Dalton Trans.

261

227

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“…In summary, by modifying the sterics and electronics of the ligands and by modulating the lanthanide ion, a few of novel heteroleptic, charge-separated heterobimetallic, and polymeric alkali metal ate complexes of 1,2,4-diazaphospholide lanthanum(III), cerium(III), neodymium(III), praseodymium(III), and samarium(III) (3)(4)(5)(6)(7)(8)(9)(10)(11)(12) were readily synthesized via the metathesis reaction of MCl 3 ⋅(THF) m (m = 1-2) and 3,5-di-substituent-1,2,4-diazaphospholide K[3,5-R 2 dp] in a varied ratio at room temperature in tetrahydrofuran. Our work therefore demonstrated that an extensive 1,2,4-diazaphoshpholide rare earth metal complexes could be accessible by this path.…”

Section: Discussionmentioning

confidence: 99%

“…As heterobimetallic lanthanide complexes are expected in the presence of excessive organo-alkali species, 10c the reaction of 1 (or 2) and SmCl 3 ·1.98THF 11 in a ratio of 4:1 was thus When treatment of MCl 3 ·mTHF (M = La, m = 1.36; M = Sm, m = 1.98) and potassium 3,5-di-phenyl-1,2,4-diazaphospholide K[3,5-Ph 2 dp] (2) 5a in a ratio 1:5 under a similar condition, two novel dipotassium ate complexes of 1,2,4-diazaphospholide lanthanide(III) (10) and samarium(III) (11) were isolated as colorless and pale yellow crystals in about 40% yields, respectively (Scheme 3). 12 Compounds 10 and 11 are fair soluble in toluene but well soluble in DMSO and THF.…”

Section: Synthesesmentioning

confidence: 99%

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1,2,4-Diazaphospholide complexes of lanthanum(iii), cerium(iii), neodymium(iii), praseodymium(iii), and samarium(iii): synthesis, X-ray structural characterization, and magnetic susceptibility studies

Zhao

Wang

et al. 2016

Dalton Trans.

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A few heteroleptic, charge-separated heterobimetallic, and polymeric alkali metalate complexes of 1,2,4-diazaphospholide lanthanum(iii), cerium(iii), neodymium(iii), praseodymium(iii), and samarium(iii) were simply prepared via the metathesis reaction of MCl3 (THF)m (m = 1-2) and K[3,5-R2dp] ([3,5-R2dp](-) = 3,5-di-substituent-1,2,4-diazaphospholide; R = tBu, Ph) in a varied ratio (1 : 3, 1 : 4, and 1 : 5, respectively) at room temperature in tetrahydrofuran. All the complexes were fully characterized by (1)H, (13)C{(1)H}, (31)P{(1)H}, IR, and X-ray single crystal diffraction analysis despite their paramagnetism (excluding La(iii) complexes). The structures of the complexes were found to feature varied coordination modes. The magnetic properties of several compounds were studied by magnetic susceptibility, and the complexes presented the magnetic moments close to or lower than the theoretical values for the free ions in the trivalent oxidation states (Pr(3+), Nd(3+)).

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“…Fu È r 1 betra È gt sie ca. 91 g´l ±1 (THF, 20°C, bezogen auf Pr(NO 3 ) 3 ), wa È hrend PrCl 3 in demselben Solvens nur eine Lo È slichkeit von 6 g´l ±1 aufweist [7]. Da u È ber THF-Komplexe von Selten-Erd-Nitraten keine Strukturdaten verfu È gbar sind, habe ich 1 mit Ro È ntgenbeugungsmethoden untersucht.…”

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Synthese von Dimethoxyethan- und Tetrahydrofuran-Komplexen der Selten-Erd-Nitrate - Festkörperstruktur von Pr(NO3)3(thf)4

Niemeyer

1999

Z. anorg. allg. Chem.

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Herstellung von Tetrahydrofuranverbindungen der Seltenerdchloride

Cited by 24 publications

References 0 publications

Synthesis and structural characterisation of rare-earth bis(dimethylsilyl)amides and their surface organometallic chemistry on mesoporous MCM-41 †

Synthesis and structural characterisation of rare-earth bis(dimethylsilyl)amides and their surface organometallic chemistry on mesoporous MCM-41 †

1,2,4-Diazaphospholide complexes of lanthanum(iii), cerium(iii), neodymium(iii), praseodymium(iii), and samarium(iii): synthesis, X-ray structural characterization, and magnetic susceptibility studies

Synthese von Dimethoxyethan- und Tetrahydrofuran-Komplexen der Selten-Erd-Nitrate - Festkörperstruktur von Pr(NO3)3(thf)4

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