TY - JOUR
T1 - Die deprotonierung silylierter amido-komplexe von seltenerdelementen
AU - Karl, Marc
AU - Harms, Klaus
AU - Seybert, Gerd
AU - Massa, Werner
AU - Stefan, Fau
AU - Frenking, Gernot
AU - Dehnicke, Kurt
PY - 1999
Y1 - 1999
N2 - The deprotonation of the rare earth element-tris-(bistrimethylsilyl)amides Ln[N(SiMe3)2]3 of scandium, ytterbium, and lutetium with sodium-bis(trimethylsilyl)amide in THF leads to the complexes [Na(THF)3LnCH2SiMe2NSiMe3 · {N(SiMe3)2}2] [Ln = Sc (1), Yb (2), and Lu (3)]. According to crystal structure analyses of 1 and 2 the metal atoms Sc and Yb are constituents of planar LnCSiN four-membered rings. At the same time, the C atom of the CH2 group is coordinated with the sodium ion in a linear axis Ln-C-Na; the sodium ion obtains a distorted tetrahedral arrangement by three THF molecules. The equatorial positions of the methylene-C atom, which is coordinated in a trigonal bipyramidal fashion, are occupied by the two H atoms and the Si atom of the four-membered ring. 2.6-dimethylbenzoisonitrile can be inserted into the Yb-CH2 bond of 2 and the new five-membered heterocylce YbNCSiN originates, the exocyclic CH2 group of which enters into a C-C coupling with the centrosymmetric dimer 4 while the ytterbium undergoes reduction. At the same time, sodium-7-methyl indolate is formed, which together with [NaN(SiMe3)2(THF)2] forms the centrosymmetric dimeric molecular aggregate [NaN(SiMe3)2(THF)2Na · (C9H16N)]2 (5). 1: Space group P21/n, Z = 8, lattice dimensions at -80 °C: a = 2941.4(2), b = 1205.5(1), c = 2952.4(3) pm; β = 113.455(8)°; R1 = 0.0625. 2: Space group P21/n, Z = 8, lattice dimensions at -80 °C: a = 2943.9(1), b = 1219.5(1), c = 2944.3(1) pm; β = 113.372(4)°; R1 =0.0361. 4: Space group P1̄, Z = 4, lattice dimensions at -80 °C: a = 1117.0(1), b = 1207.5(1), c = 1614.3(2) pm; α= 73.634(10)°, β = 82.091 (10)°, γ = 74.391(10)°; R1 = 0.0525. 5: Space group P21/n, Z = 2, lattice dimensions at -80 °C: a = 1126.7(1), b = 1459.3(1), c = 1741.1(1) pm; β = 96.461(8)°; R1 = 0.0458. Quantum chemical DFT calculations of the scandium model compound [Na(Me2O)3ScCH2SiMe2NSiH 3{N(SiH3)2}2] (1 M) give a very large negative charge at the pentacoordinated carbon atom of the four-membered ring that is concentrated in a lone-pair orbital which has mainly p character. The carbon atom interacts with the positively charged scandium atom mainly by Coulombic interactions.
AB - The deprotonation of the rare earth element-tris-(bistrimethylsilyl)amides Ln[N(SiMe3)2]3 of scandium, ytterbium, and lutetium with sodium-bis(trimethylsilyl)amide in THF leads to the complexes [Na(THF)3LnCH2SiMe2NSiMe3 · {N(SiMe3)2}2] [Ln = Sc (1), Yb (2), and Lu (3)]. According to crystal structure analyses of 1 and 2 the metal atoms Sc and Yb are constituents of planar LnCSiN four-membered rings. At the same time, the C atom of the CH2 group is coordinated with the sodium ion in a linear axis Ln-C-Na; the sodium ion obtains a distorted tetrahedral arrangement by three THF molecules. The equatorial positions of the methylene-C atom, which is coordinated in a trigonal bipyramidal fashion, are occupied by the two H atoms and the Si atom of the four-membered ring. 2.6-dimethylbenzoisonitrile can be inserted into the Yb-CH2 bond of 2 and the new five-membered heterocylce YbNCSiN originates, the exocyclic CH2 group of which enters into a C-C coupling with the centrosymmetric dimer 4 while the ytterbium undergoes reduction. At the same time, sodium-7-methyl indolate is formed, which together with [NaN(SiMe3)2(THF)2] forms the centrosymmetric dimeric molecular aggregate [NaN(SiMe3)2(THF)2Na · (C9H16N)]2 (5). 1: Space group P21/n, Z = 8, lattice dimensions at -80 °C: a = 2941.4(2), b = 1205.5(1), c = 2952.4(3) pm; β = 113.455(8)°; R1 = 0.0625. 2: Space group P21/n, Z = 8, lattice dimensions at -80 °C: a = 2943.9(1), b = 1219.5(1), c = 2944.3(1) pm; β = 113.372(4)°; R1 =0.0361. 4: Space group P1̄, Z = 4, lattice dimensions at -80 °C: a = 1117.0(1), b = 1207.5(1), c = 1614.3(2) pm; α= 73.634(10)°, β = 82.091 (10)°, γ = 74.391(10)°; R1 = 0.0525. 5: Space group P21/n, Z = 2, lattice dimensions at -80 °C: a = 1126.7(1), b = 1459.3(1), c = 1741.1(1) pm; β = 96.461(8)°; R1 = 0.0458. Quantum chemical DFT calculations of the scandium model compound [Na(Me2O)3ScCH2SiMe2NSiH 3{N(SiH3)2}2] (1 M) give a very large negative charge at the pentacoordinated carbon atom of the four-membered ring that is concentrated in a lone-pair orbital which has mainly p character. The carbon atom interacts with the positively charged scandium atom mainly by Coulombic interactions.
KW - Deprotonation Reactions
KW - Insertion of Isonitril
KW - Lutetium
KW - Rare Earth Elements
KW - Scandium
KW - Ytterbium
UR - http://www.scopus.com/inward/record.url?scp=0000383759&partnerID=8YFLogxK
U2 - 10.1002/(sici)1521-3749(199912)625:12<2055::aid-zaac2055>3.0.co;2-y
DO - 10.1002/(sici)1521-3749(199912)625:12<2055::aid-zaac2055>3.0.co;2-y
M3 - 文章
AN - SCOPUS:0000383759
SN - 0044-2313
VL - 625
SP - 2055
EP - 2063
JO - Zeitschrift fur Anorganische und Allgemeine Chemie
JF - Zeitschrift fur Anorganische und Allgemeine Chemie
IS - 12
ER -