(2,5‐Bis{[(2,6‐diisopropylphenyl)imino]methyl}pyrrolyl)yttrium and ‐lutetium Complexes – Synthesis and Structures

Meyer, Nils; Kuzdrowska, Magdalena; Roesky, Peter W.

doi:10.1002/ejic.200701238

Cited by 20 publications

(27 citation statements)

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“…[32] It is well known that Schiff base ligands such as bisA C H T U N G T R E N N U N G (imino)pyridines are noninnocent lig-A C H T U N G T R E N N U N G ands that can be alkylated at the imino function by alkyl complexes. [33][34][35][36] [37,38] Herein, we present a full account of the reaction of the…”

Section: Introductionmentioning

confidence: 99%

Borane and Borohydride Complexes of the Rare‐Earth Elements: Synthesis, Structures, and Butadiene Polymerization Catalysis

Jenter

Meyer

Roesky

et al. 2010

Chemistry A European J

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The reaction of potassium 2,5-bis[N-(2,6-diisopropylphenyl)iminomethyl]pyrrolyl [(dip(2)-pyr)K] with the borohydrides of the larger rare-earth metals, [Ln(BH(4))(3)(thf)(3)] (Ln=La, Nd), afforded the expected products [Ln(BH(4))(2)(dip(2)-pyr)(thf)(2)]. As usual, the trisborohydrides reacted like pseudohalide compounds forming KBH(4) as a by-product. To compare the reactivity with the analogous halides, the dimeric neodymium complex [NdCl(2)(dip(2)-pyr)(thf)](2) was prepared by reaction of [(dip(2)-pyr)K] with anhydrous NdCl(3). Reaction of [(dip(2)-pyr)K] with the borohydrides of the smaller rare-earth metals, [Sc(BH(4))(3)(thf)(2)] and [Lu(BH(4))(3)(thf)(3)], resulted in a redox reaction of the BH(4) (-) group with one of the Schiff base functions of the ligand. In the resulting products, [Ln(BH(4)){(dip)(dip-BH(3))-pyr}(thf)(2)] (Ln=Sc, Lu), a dinegatively charged ligand with a new amido function, a Schiff base, and the pyrrolyl function is bound to the metal atom. The by-product of the reaction of the BH(4) (-) anion with the Schiff base function (a BH(3) molecule) is trapped in a unique reaction mode in the coordination sphere of the metal complex. The BH(3) molecule coordinates in an eta(2) fashion to the metal atom. The rare-earth-metal atoms are surrounded by the eta(2)-coordinated BH(3) molecule, the eta(3)-coordinated BH(4) (-) anion, two THF molecules, and the nitrogen atoms from the Schiff base and the pyrrolyl function. All new compounds were characterized by single-crystal X-ray diffraction. Low-temperature X-ray diffraction data at 6 K were collected to locate the hydrogen atoms of [Lu(BH(4)){(dip)(dip-BH(3))-pyr}(thf)(2)]. The (DIP(2)-pyr)(-) borohydride and chloride complexes of neodymium, [Nd(BH(4))(2)(dip(2)-pyr)(thf)(2)] and [NdCl(2)(dip(2)-pyr)(thf)](2), were also used as Ziegler-Natta catalysts for the polymerization of 1,3-butadiene to yield poly(cis-1,4-butadiene). Very high activities and good cis selectivities were observed by using each of these complexes as a catalyst in the presence of various cocatalyst mixtures.

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Section: Introductionmentioning

confidence: 99%

Borane and Borohydride Complexes of the Rare‐Earth Elements: Synthesis, Structures, and Butadiene Polymerization Catalysis

Jenter

Meyer

Roesky

et al. 2010

Chemistry A European J

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“…Treatment of 5 with NaH or KH in hot THF afforded [(DIP 2 pyr)M] (M = Na (7), K (8)) (Scheme 4) [10].…”

Section: Methodsmentioning

confidence: 99%

New Development in Rare Earth Metal Complexes Containing Anionic Bis(imino)pyrrolyl and Bis(phosphanyl)amide Ligands

Jenter

Roesky

2010

Zeitschrift anorg allge chemie

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“…However, Fryzuk and co-workers found success with their so-called NPN diamidophosphine pincer (Scheme 43) [87]. The dilithiated salt of this ligand reacts readily with the THF adducts of yttrium, samarium, holmium, ytterbium, and lutetium trichloride to give the desired halide complexes LLn(Cl)(THF) (Ln ¼ Y, Sm, Ho, Yb, Lu; L ¼ PhP Mixed pincer-Cp complexes featuring an NNN-bis(iminomethyl)pyrrolyl ligand were reported by Roesky and colleagues [88]. Initial efforts to prepare well-behaved dihalide complexes of this ligand by the reaction of the lithium salt of the ligand with YCl 3 in THF proceeded to the "ate" complex LYCl 2 3 (Ln ¼ La, Lu) as the starting materials (Scheme 44) [11].…”

Section: Alkylation By Organoalkali Compoundsmentioning

confidence: 96%

Rare Earth Pincer Complexes: Synthesis, Reaction Chemistry, and Catalysis

Hänninen

Zamora

Hayes

2015

The Privileged Pincer-Metal Platform: Coordination Chemistry &Amp; Applications

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The research field surrounding rare earth pincer complexes has reached a stage where a comprehensive review about the reactivity and catalytic behavior of these species is justified. In this contribution, we begin with a brief introduction on common strategies for the preparation of rare earth pincer complexes, continuing with a section devoted to the versatile reactivity observed for this class of compound. Thereafter, several types of compounds are discussed, including extremely reactive hydrides, cationic species, and intriguing scandium imido complexes. Finally, the last portion of this chapter sums up the hitherto reported catalytic studies, including discussions on ring-opening polymerization of cyclic esters, polymerization of olefins and hydroamination reactions, as well as several examples of more infrequently encountered catalytic processes.

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(2,5‐Bis{[(2,6‐diisopropylphenyl)imino]methyl}pyrrolyl)yttrium and ‐lutetium Complexes – Synthesis and Structures

Abstract: Keywords: Lutetium / N ligands / Potassium / Pyrrole / Yttrium

Cited by 20 publications

References 20 publications

Borane and Borohydride Complexes of the Rare‐Earth Elements: Synthesis, Structures, and Butadiene Polymerization Catalysis

Borane and Borohydride Complexes of the Rare‐Earth Elements: Synthesis, Structures, and Butadiene Polymerization Catalysis

New Development in Rare Earth Metal Complexes Containing Anionic Bis(imino)pyrrolyl and Bis(phosphanyl)amide Ligands

Rare Earth Pincer Complexes: Synthesis, Reaction Chemistry, and Catalysis

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