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

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Framework Solids Possessing Both Hydrophobic and Hydrophilic Pores Constructed by Face-Sharing Keplerate-Type Heterometal–Organic Polyhedra

Boronic Acid Catalysis for Mild and Selective [3+2] Dipolar Cycloadditions to Unsaturated Carboxylic Acids

Surface-Modified Upconverting Microparticles and Nanoparticles for Use in Click Chemistries

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Asymmetric Organocatalytic Rearrangement Reactions

Programmed-Assembly System Using DNA Jigsaw Pieces

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

Transition-Metal-Catalyzed Synthesis of Hydroxylated Arenes

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

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Meyer, Nils Jenter, Jelena Eickerling, Georg Thiele, Sven K-h Scherer, Wolfgang Roesky, Peter W.
Description	Author Affiliation: Jenter J ( Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT), Engesserstr. 15, 76131 Karlsruhe, Germany.)
Abstract	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 $η^{2}$ fashion to the metal atom. The rare-earth-metal atoms are surrounded by the $η^{2}-coordinated$ $BH_{3}$ molecule, the $η^{3}-coordinated$ $BH_{4}^{−}$ 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.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	18
Volume Number	16
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2010-05-10
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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