TY - JOUR
T1 - Highly Reactive Organolanthanides. Synthesis, Chemistry, and Structures of 4f Hydrocarbyls and Hydrides with Chelating Bis(polymethylcyclopentadienyl) Ligands
AU - Jeske, Gerald
AU - Schock, Laurel E.
AU - Swepston, Paul N.
AU - Schumann, Herbert
AU - Marks, Tobin J.
N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 1985/12
Y1 - 1985/12
N2 - This contribution discusses lanthanide hydrocarbyl and hydride chemistry based upon Me2SiCp“2supporting ligation (Cp“ = 7/5-(CFf34C5). The reaction of MC13, M = Nd, Sm, or Lu, with Me2Si(Cp“Li)2yields the precursor complexes Me2SiCp”2MCl2_Li(ether)2+. A slightly different workup procedure yielded (Me2SiCp“2NdCl)2Cl“Li(THF)2+, which crystallizes in the monoclinic space group P2/n with two molecules in a unit cell of dimensions (-133 °C) a = 11.666 (3) Å, b= 12.585 (3) Å, c = 17.765 (6) Å, and β = 94.91 (2)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.045 for 3231 independent reflections having I > 3σ(I). The structure consists of two Me2Si(η5-Cp”)2Nd units bridged by a chloride ion and an Nd-Cl-.Li+.Cl-Nd linkage. The Nd-Cl distances are 2.802 (1) and 2.754 (2) Å, and ∠Cl-Nd-Cl = 97.1 (1)°. The (ring centroid)-Nd-(ring centroid) angle is 121.3°. The Nd-C(ring) distances vary from 2.647 (7) to 2.815 (7) A, with the shorter distances being to those carbon atoms closest to the Me2Si bridge. The Me2SiCp“2MCl2compounds react with LiCH[Si(CH33]2to yield ether- and halide-free Me2SiCp“2MCH[Si(CH33]2derivatives. The M = Nd compound crystallizes in the monoclinic space group P21/n with four molecules in a cell of dimensions (-125 °C) a = 10.229 (2) Å, b = 15.623 (3) Å, c = 19.687 (3) Å, and β = 105.41 (2)°. Least-squares refinement led to a value of the conventional R index (on F) of 0.044 for 3407 independent, absorption corrected reflections having I> 3σ(I). The molecular structure consists of monomeric Me2SiCp”2NdCH[Si(CH33]2units with η5-Cp“ coordination, and ∠(ring centroid)-Nd-(ring centroid) = 121.6°. The CH[Si(CH33]2fragment is coordinated to the Me2SiCp“2Nd center in a highly unsymmetrical fashion with a Nd-C σ-bond distance of 2.506 (7) Å and a secondary interaction to one methyl group of Nd-C = 2.862 (8) Å. The Si-C distance to this carbon atom is significantly longer than the other Si-CH3contacts. Approximate hydrogen atom locations argue against an important M—HC(methyl) interaction and reveal a bending of the hydrogen atom on the σ-bonded carbon atom toward the metal with ∠Nd-C-H ~ 76°. Reaction of the Me2SiCp“2MCH[Si(CH33]2complexes with H2yields the coresponding hydrides, which are formulated as Me2SiCp“2M(μ-H)2MCp“2SiMe2dimers. These compounds are active agents for the polymerization of ethylene as well as for the oligomerization of propylene and 1-hexene. For a constant lanthanide ion, a (Me2SiCp“2MH)2hydride is an ca. 10 times more active for this reaction than the corresponding (Cp'2MH)2hydride. Deprotonation of Me2SiCp”2LuCH(TMS)2with t-BuLi/TMEDA leads to a metallacycle formulated as Li(TMEDA)3+-Me2SiCp“2LuCH2Si(CH32C(H)Si(CH23-.
AB - This contribution discusses lanthanide hydrocarbyl and hydride chemistry based upon Me2SiCp“2supporting ligation (Cp“ = 7/5-(CFf34C5). The reaction of MC13, M = Nd, Sm, or Lu, with Me2Si(Cp“Li)2yields the precursor complexes Me2SiCp”2MCl2_Li(ether)2+. A slightly different workup procedure yielded (Me2SiCp“2NdCl)2Cl“Li(THF)2+, which crystallizes in the monoclinic space group P2/n with two molecules in a unit cell of dimensions (-133 °C) a = 11.666 (3) Å, b= 12.585 (3) Å, c = 17.765 (6) Å, and β = 94.91 (2)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.045 for 3231 independent reflections having I > 3σ(I). The structure consists of two Me2Si(η5-Cp”)2Nd units bridged by a chloride ion and an Nd-Cl-.Li+.Cl-Nd linkage. The Nd-Cl distances are 2.802 (1) and 2.754 (2) Å, and ∠Cl-Nd-Cl = 97.1 (1)°. The (ring centroid)-Nd-(ring centroid) angle is 121.3°. The Nd-C(ring) distances vary from 2.647 (7) to 2.815 (7) A, with the shorter distances being to those carbon atoms closest to the Me2Si bridge. The Me2SiCp“2MCl2compounds react with LiCH[Si(CH33]2to yield ether- and halide-free Me2SiCp“2MCH[Si(CH33]2derivatives. The M = Nd compound crystallizes in the monoclinic space group P21/n with four molecules in a cell of dimensions (-125 °C) a = 10.229 (2) Å, b = 15.623 (3) Å, c = 19.687 (3) Å, and β = 105.41 (2)°. Least-squares refinement led to a value of the conventional R index (on F) of 0.044 for 3407 independent, absorption corrected reflections having I> 3σ(I). The molecular structure consists of monomeric Me2SiCp”2NdCH[Si(CH33]2units with η5-Cp“ coordination, and ∠(ring centroid)-Nd-(ring centroid) = 121.6°. The CH[Si(CH33]2fragment is coordinated to the Me2SiCp“2Nd center in a highly unsymmetrical fashion with a Nd-C σ-bond distance of 2.506 (7) Å and a secondary interaction to one methyl group of Nd-C = 2.862 (8) Å. The Si-C distance to this carbon atom is significantly longer than the other Si-CH3contacts. Approximate hydrogen atom locations argue against an important M—HC(methyl) interaction and reveal a bending of the hydrogen atom on the σ-bonded carbon atom toward the metal with ∠Nd-C-H ~ 76°. Reaction of the Me2SiCp“2MCH[Si(CH33]2complexes with H2yields the coresponding hydrides, which are formulated as Me2SiCp“2M(μ-H)2MCp“2SiMe2dimers. These compounds are active agents for the polymerization of ethylene as well as for the oligomerization of propylene and 1-hexene. For a constant lanthanide ion, a (Me2SiCp“2MH)2hydride is an ca. 10 times more active for this reaction than the corresponding (Cp'2MH)2hydride. Deprotonation of Me2SiCp”2LuCH(TMS)2with t-BuLi/TMEDA leads to a metallacycle formulated as Li(TMEDA)3+-Me2SiCp“2LuCH2Si(CH32C(H)Si(CH23-.
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U2 - 10.1021/ja00312a051
DO - 10.1021/ja00312a051
M3 - Article
AN - SCOPUS:33845379315
VL - 107
SP - 8103
EP - 8110
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 26
ER -