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Jenter J, Meyer N, Roesky PW, et al. Borane and borohydride complexes of the rare-earth elements: synthesis, structures, and butadiene polymerization catalysis. Chemistry. 2010;16(18):5472-80doi: 10.1002/chem.200902923.
Jenter, J., Meyer, N., Roesky, P. W., Thiele, S. K., Eickerling, G., & Scherer, W. (2010). Borane and borohydride complexes of the rare-earth elements: synthesis, structures, and butadiene polymerization catalysis. Chemistry (Weinheim an der Bergstrasse, Germany), 16(18), 5472-80. https://doi.org/10.1002/chem.200902923
Jenter, Jelena, et al. "Borane and borohydride complexes of the rare-earth elements: synthesis, structures, and butadiene polymerization catalysis." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 16,18 (2010): 5472-80. doi: https://doi.org/10.1002/chem.200902923
Jenter J, Meyer N, Roesky PW, Thiele SK, Eickerling G, Scherer W. Borane and borohydride complexes of the rare-earth elements: synthesis, structures, and butadiene polymerization catalysis. Chemistry. 2010 May 10;16(18):5472-80. doi: 10.1002/chem.200902923. PMID: 20397155.
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Chemistry. 2010 May 10;16(18):5472-80. doi: 10.1002/chem.200902923.

Borane and borohydride complexes of the rare-earth elements: synthesis, structures, and butadiene polymerization catalysis.

Chemistry (Weinheim an der Bergstrasse, Germany)

Jelena Jenter, Nils Meyer, Peter W Roesky, Sven K-H Thiele, Georg Eickerling, Wolfgang Scherer

Affiliations

  1. Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT), Engesserstr. 15, 76131 Karlsruhe, Germany.

PMID: 20397155 DOI: 10.1002/chem.200902923

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 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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