Synthesis and Reactivity of Bis(phospholyl)neodymium(III) and -samarium(III) Chlorides and Alkyl Derivatives

Nief, François; Riant, Philippe; Ricard, Louis; Desmurs, Pascale; Baudry-Barbier, Denise

doi:10.1002/(sici)1099-0682(199906)1999:6<1041::aid-ejic1041>3.3.co;2-5

Cited by 6 publications

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“… Formation of 3 as an “ate” complex can be easily rationalized by the much weaker electron-donating ability of the C 4 Me 4 P ligand compared with the isosteric Cp* group. This distinct property of the phospholyl ligand had been clearly illustrated by the redox behavior and coordination chemistry of a variety of uranium compounds. , Complex 3 is a new example of a bis(phospholyl) lanthanide(III) derivative, which include [(C 4 Me 4 P) 2 LnCl 2 ] - (Ln = Y, Nd, Sm, Lu), (C 4 Me 4 P) 2 Ln(CH{SiMe 3 } 2 ) (Ln = Nd, Sm), and (C 4 Me 4 P) 2 NdH . Complexes 2 and 3 also represent the only organometallic bis-borohydride derivatives of a lanthanide(III).…”

Section: Resultsmentioning

confidence: 99%

Lanthanide Borohydrides as Precursors to Organometallic Compounds. Mono(cyclooctatetraenyl) Neodymium Complexes

et al. 2000

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Section: Resultsmentioning

confidence: 99%

Lanthanide Borohydrides as Precursors to Organometallic Compounds. Mono(cyclooctatetraenyl) Neodymium Complexes

et al. 2000

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“…Eine Übersicht von 1998 fasst Komplexe mit den Zentralatomen Ti, Mn, Fe, Co, Ni, Zr, Mo, Ru, Rh, W, Re, Y, Sm, Yb, Lu und U zusammen 254b. Jüngst kamen Ga,257 Tl,258 Hf,259 Ge,260 Sn,260 Pb,260 Cr,261 Ir,262 Nd263 und Tm264 hinzu, und des Weiteren wurden einige η 5 ‐Komplexe mit Alkali‐ und Erdalkalimetallen, darunter Na,265 K,265 Cs,266 Ca267 und Ba,268 strukturell charakterisiert.…”

Section: Besondere Elektronenkonfigurationenunclassified

Phosphaorganische Chemie: Panorama und Perspektiven

Mathey

2003

Angewandte Chemie

198

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Die gesamte phosphororganische Chemie wurde mit Beginn der siebziger Jahre infolge der Entdeckung stabiler phosphororganischer Derivate mit Koordinationszahlen des Phosphors von 1 oder 2 aufgefrischt. Bezüglich ihrer Chemie gleichen diese Verbindungen ihren reinen Kohlenstoff‐Analoga. Dieser Aufsatz widmet sich der Analogie zwischen den Phosphorderivaten und den entsprechenden Alkenen, Alkinen und Carbenen, wobei jede Verbindungsklasse anhand ihrer Synthese, ihrer Reaktivität und ihres Koordinationstyps kurz vorgestellt wird. Des Weiteren werden besondere Elektronenkonfigurationen der Phosphorverbindungen behandelt, darunter P‐P‐Einelektronenbindungen, gespannte Bindungen und aromatische Systeme. Abschließend wird auf mögliche Anwendungen dieser Chemie zur Herstellung molekularer Materialien und in der homogenen Katalyse verwiesen.

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“…25 Surprisingly, none of these complexes retained any solvent-salt molecules, i.e., "ate"-type complexes were not formed. "Ate" complex formation is commonly seen with the lanthanides [26][27][28][29][30][31][32][33][34] and early transition metals. [35][36][37][38][39][40] Similar retention of solvent-salt adducts has also been reported for actinide complexes containing ansa-cyclopentadienyl-amido ligands, 41 cyclopentadienyl-type ligands, 42-45 permethylindenyl 46 and [(-CH 2 -) 5 ]-4-calix [4]tetrapyrrole ligands.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and structure of diamido ether uranium(iv) and thorium(iv) halide “ate” complexes and their conversion to salt-free bis(alkyl) complexes

et al. 2005

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The high-yield synthesis, spectroscopic and structural determination of three new uranium(IV) and thorium(IV)ate complexes supported by three different diamido ether ligands are reported. The reaction of Li2[2,6-iPr2PhN(CH2CH2)]2O (Li2[DIPPNCOCN]) with 1 equiv. of UCl4 in THF generates [DIPPNCOCN]UCl3Li(THF)2(1), while reaction in toluene/ether gives salt-free [DIPPNCOCN]UCl2.1/2C7H8(2), which was identified by paramagnetically shifted 1H NMR. Reaction of 0.5 equiv. of {[tBuNON]UCl2}2([tBuNON]=[(CH3)3CN(Si(CH3)2)]2O2-) with 3.5 equiv. LiI in toluene and a minimal amount of THF results in [tBuNON]UI3Li(THF)2(3) and is very similar in structure to 1. {[MesNON]ThCl3Li(THF)}2(4), a dimeric complex with a Th2Li2Cl6 core, is prepared by reaction of Li2[2,4,6-Me3PhN(Si(CH3)2)]2O (Li2[MesNON]) with ThCl4 in THF. The analogous reaction in toluene did not yield the salt-free complex but rather a sterically crowded diligated compound, [MesNON]2Th (5), which was also structurally characterized. Complex 5 was prepared rationally by reacting 2 equiv. Li2[MesNON] with ThCl4 in toluene. The reaction of 1 and 3 with 2 equiv. of LiCH2Si(CH3)3 generates the stable, salt-free organoactinides [DIPPNCOCN]U(CH2Si(CH3)3)2(6) and [tBuNON]U(CH2Si(CH3)3)2(7). Complex 6 was structurally characterized. These reactions illustrate the viability of ate complexes as useful synthetic precursors.

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Synthesis and Reactivity of Bis(phospholyl)neodymium(III) and -samarium(III) Chlorides and Alkyl Derivatives

Cited by 6 publications

References 0 publications

Lanthanide Borohydrides as Precursors to Organometallic Compounds. Mono(cyclooctatetraenyl) Neodymium Complexes

Lanthanide Borohydrides as Precursors to Organometallic Compounds. Mono(cyclooctatetraenyl) Neodymium Complexes

Phosphaorganische Chemie: Panorama und Perspektiven

Synthesis and structure of diamido ether uranium(iv) and thorium(iv) halide “ate” complexes and their conversion to salt-free bis(alkyl) complexes

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