On the synthesis of monopentamethylcyclopentadienyl derivatives of yttrium, lanthanum, and cerium

Booij, Marianne; Kiers, Niklaas H.; Heeres, Hero J.; Teuben, Jan H.

doi:10.1016/0022-328x(89)85333-1

Cited by 91 publications

(47 citation statements)

References 28 publications

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“…8 These compounds have often been overlooked, primarily for two reasons: (1) due to the electrophilicity of the lanthanides, common synthetic routes often result in the non-stoichiometric incorporation of salt molecules into the coordination sphere of the metal, resulting in 'ate' complexes; 9 -19 (2) the high degree of steric unsaturation in these complexes often leads to disproportionation of CpLnX 2 species to Cp 2 LnX and LnX 3 (Cp = cyclopentadienyl or cyclopentadienyl derivative; Ln = lanthanide; X = halide, alkyl, aryloxide, amide). 17,20,21 Recently, work by us 22 and others 23 -25 has shown that, by employing potassium salts of C 5 Me 5 and lanthanide tri-iodides, mono-ring species that are free from additional salt complexation may be obtained, although there are still only a handful of CpLnI 2 L x (L = Lewis…”

Section: Introductionmentioning

confidence: 98%

Syntheses and structures of mono‐cyclopentadienyl di‐iodide complexes of the lanthanides: X‐ray crystal structures of Cp‴LaI₂py₃ (Cp‴ = [η⁵‐C₅H₂(SiMe₃)₃‐1,2,4]⁻; py = pyridine) and Cp‴LaI₂(bipy)py (bipy = 2, 2′‐bipyridine)

Giesbrecht

Clark

Gordon

et al. 2003

Applied Organom Chemis

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Section: Introductionmentioning

confidence: 98%

Syntheses and structures of mono‐cyclopentadienyl di‐iodide complexes of the lanthanides: X‐ray crystal structures of Cp‴LaI₂py₃ (Cp‴ = [η⁵‐C₅H₂(SiMe₃)₃‐1,2,4]⁻; py = pyridine) and Cp‴LaI₂(bipy)py (bipy = 2, 2′‐bipyridine)

Giesbrecht

Clark

Gordon

et al. 2003

Applied Organom Chemis

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“…3 (Ln＝La, Ce) [118] . 采用(C 5 Me 5 ) -作配体可以合成得到单茂轻稀土二氯化物 [119] 和二碘化物 [120] . Watson 等在研究二价镱配图 11 1,1'-(氧代-五亚甲基)双环戊二烯基稀土氢化物的合成 Figure 11 Synthesis of 1,1'-(3-Oxa-pentamethylene) dicyclopentadienyl rare-earth metal hydrides [121] , Br [122] ).…”

Section: 二茂稀土金属氢化物过渡金属氢化物在很多重要有机化学反应中被用作试剂和催化剂它们的合成和反应化学在金属有机化学中unclassified

Sixty Years of the Chemistry of Rare-earth Organometallic Complexes

Changtao¹,

Wang²,

Chen³

2014

Acta Chim. Sinica

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Rare-earth elements include scandium, yttrium and fifteen lanthanides. Since Wilkinson and Birmingham reported the fist example of rare-earth organometallic complex, the chemistry of rare-earth organometallic complexes has had a great advance during the past sixty years. A variety of Cp containing rare-earth metal complexes, including mono-Cp, bis-Cp, and tri-Cp complexes, have been synthesized. Variation of the size of substituent on Cp ring, introducing the nitrogen or oxygen containing pendant arm to Cp ring or using ansa bis-Cp ligands make the synthesis and stabilization of these three types of rare-earth metal Cp complexes available. The Cp related ligands, such as indenyl and fluorenyl, also have been applied for the rare-earth organometallic complexes. From 1990's, there was a tendency to explore the rare-earth organometallic complexes with ancillary ligands beyond Cp and its derivatives in order to search for more efficient rare-earth metal catalysts. Non-Cp ligands, such as biphenolates, β-diketiminates, amidinates, guanidinates, etc. have been introduced into the chemistry of rare-earth organometallic complexes, and a larger number of non-Cp rare-earth organometallic complexes have been synthesized and characterized. The application of non-cyclopentadienyl ligands not only resulted in the rare-earth organometallic complexes with new structural features, but also the catalysts with high activity and high selectivity for the polymer synthesis and organic synthesis. The rare-earth organometallic complexes catalyze homo-and co-polymerization of olefins as well as specific polymerization of dienes and polar monomers. The discovery of the catalytic system composed of the neutral rare-earth metal dialkyls/borate enables to synthesize some interesting polymers which are difficult to be prepared by using other catalytic system. The rare-earth organometallic complexes are also able to catalyze some important organic reactions, such as hydroamination, hydrophosphinylation, and hydroalkoxylation, etc. Different from the late-translation metal catalyzed organic reactions, most of the rare-earth metal catalyzed ones do not involve oxidative addition and reductive elimination steps. The review describes some important developments of the chemistry of rare-earth organometallic complexes in the past sixty years.

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“…However, desolvation and clustering were observed, leading to the formation of hexamers [(C 5 Me 4 nPr)Ln(BH 4 ) 2 ] 6 as the crystalline form [9]. On the other hand, the s-bond metathesis method allows the straightforward formation of the expected product, but it requires highly sensitive homoleptic LnR 3 precursors (R ¼ alkyl [2], allyl [10], phenyl [11], or amido group [12]) [13]. Moreover, owing to the basicity of the R group, heating is often necessary to achieve the metathesis reaction, and ligand scrambling may be not completely excluded [5,11].…”

Section: Introductionmentioning

confidence: 99%

One-pot synthesis of an ionic half-sandwich complex of neodymium. Application to isoprene polymerisation catalysis

Visseaux

Terrier

Mortreux

et al. 2007

Comptes Rendus. Chimie

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The reaction of one equivalent of Nd(BH 4 ) 3 (THF) 3 with an half equivalent of dialkylmagnesium in the presence of a stoichiometric amount of pentamethylcyclopentadiene cleanly affords a new kind of half-sandwich of neodymium that is stable toward comproportionation. This strategy can be advantageously applied to generate in situ catalysts allowing the controlled polymerisation of isoprene. To cite this article: M. Visseaux et al., C. R. Chimie 10 (2007). Ó 2007 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved. RésuméLa réaction d'un équivalent de Nd(BH 4 ) 3 (THF) 3 avec un demi-équivalent de dialkylmagnesium en présence d'une quantité stoechiométrique de pentamethylcyclopentadiène conduit de façon univoque à un hémimétallocène de néodyme d'un nouveau type, stable vis-à-vis de la comproportionation. Cette statégie peut être appliquée de façon avantageuse pour générer in situ des catalyseurs permettant la polymérisation contrôlée de l'isoprène. Pour citer cet article : M. Visseaux et al., C. R. Chimie 10 (2007).

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On the synthesis of monopentamethylcyclopentadienyl derivatives of yttrium, lanthanum, and cerium

Cited by 91 publications

References 28 publications

Syntheses and structures of mono‐cyclopentadienyl di‐iodide complexes of the lanthanides: X‐ray crystal structures of Cp‴LaI₂py₃ (Cp‴ = [η⁵‐C₅H₂(SiMe₃)₃‐1,2,4]⁻; py = pyridine) and Cp‴LaI₂(bipy)py (bipy = 2, 2′‐bipyridine)

Syntheses and structures of mono‐cyclopentadienyl di‐iodide complexes of the lanthanides: X‐ray crystal structures of Cp‴LaI₂py₃ (Cp‴ = [η⁵‐C₅H₂(SiMe₃)₃‐1,2,4]⁻; py = pyridine) and Cp‴LaI₂(bipy)py (bipy = 2, 2′‐bipyridine)

Sixty Years of the Chemistry of Rare-earth Organometallic Complexes

One-pot synthesis of an ionic half-sandwich complex of neodymium. Application to isoprene polymerisation catalysis

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On the synthesis of monopentamethylcyclopentadienyl derivatives of yttrium, lanthanum, and cerium

Cited by 91 publications

References 28 publications

Syntheses and structures of mono‐cyclopentadienyl di‐iodide complexes of the lanthanides: X‐ray crystal structures of Cp‴LaI2py3 (Cp‴ = [η5‐C5H2(SiMe3)3‐1,2,4]−; py = pyridine) and Cp‴LaI2(bipy)py (bipy = 2, 2′‐bipyridine)

Syntheses and structures of mono‐cyclopentadienyl di‐iodide complexes of the lanthanides: X‐ray crystal structures of Cp‴LaI2py3 (Cp‴ = [η5‐C5H2(SiMe3)3‐1,2,4]−; py = pyridine) and Cp‴LaI2(bipy)py (bipy = 2, 2′‐bipyridine)

Sixty Years of the Chemistry of Rare-earth Organometallic Complexes

One-pot synthesis of an ionic half-sandwich complex of neodymium. Application to isoprene polymerisation catalysis

Contact Info

Product

Resources

About

Syntheses and structures of mono‐cyclopentadienyl di‐iodide complexes of the lanthanides: X‐ray crystal structures of Cp‴LaI₂py₃ (Cp‴ = [η⁵‐C₅H₂(SiMe₃)₃‐1,2,4]⁻; py = pyridine) and Cp‴LaI₂(bipy)py (bipy = 2, 2′‐bipyridine)

Syntheses and structures of mono‐cyclopentadienyl di‐iodide complexes of the lanthanides: X‐ray crystal structures of Cp‴LaI₂py₃ (Cp‴ = [η⁵‐C₅H₂(SiMe₃)₃‐1,2,4]⁻; py = pyridine) and Cp‴LaI₂(bipy)py (bipy = 2, 2′‐bipyridine)