Jörg Loebel

Synthesis and crystal structure of pentabenzylcyclopentadienylindium(I)

Abstract (PhCH 2 ) 5 C 5 In 1 ( 1 ) is formed in the reaction between InCl and (PhCH 2 ) 5 C 5 Li. 1 crystallizes in the space group P 2 1 / c with a 1022.8(1), b 1575.3(2), c 1871.3(3) pm, β 91.01(1)°, and V 3014.6 × 10 −30 m 3 . The crystal and molecular structure was solved to final values of R = 0.025 for 5545 observed reflections with F 0 ≥ 4σ ( F 0 ). The association of two single molecules, via a center of symmetry between the two In atoms, gives the impression of quasi-“dimeric” units with an InIn distance of 363.1 pm and predominantly covalent InC. 1 H NMR, 13 C NMR, infrared and mass spectroscopic data are reported.

Synthesis and structure of Fe[C5(CH2Ph)5]2 and Lu(C8H8)[C5(CH2Ph)5]

Abstract The crystal structures of decabenzylferrocene, Fe[C 5 (CH 2 Ph) 5 ] 2 ( 1 ), obtained from FeCl 2 and LiC 5 (CH 2 Ph) 5 at low temperature and (cyclooctatetraenyl)(pentabenzylcyclopentadienyl)lutetium, Lu(C 8 H 8 )[C 5 (CH 2 Ph) 5 ] ( 2 ), obtained from (C 8 H 8 )LuCl(thf) and KC 5 (CH 2 Ph) 5 ( 3 ), have been determined. 1 crystallizes in the space group P 2 1 / c with a 1388.5(2), b 2213.1(6), c 2373.0(3) pm, β 103.50(1)°, and V = 7.0905 × 10 6 pm 3 . Solution of the structure led to final values of R = 0.043 (unit weights) for 11181 observed reflections with F o ≥ 6σ( F o ). Crystals of 2 belong to the space group P 2 1 / a . The unit-cell parameters for 2 are a 1799.0(2), b 1030.2(1), c 1902.3(2) pm, β 97.41(1)°, V = 3.4962 × 10 6 pm 3 with final values of R = 0.021 and R w = 0.030 for 7453 observed reflections with F o ≥ 3σ( F o .

SYNTHESIS, MAGNETIC SUSCEPTIBILITY AND X-RAY CRYSTAL STRUCTURE OF (TBUNCHCHNTBU)3YB

Abstract The reaction of (C 10 H 8 )Yb(THF) 3 with t BuNCHCHN t Bu ( t Budad) in tetrahydrofuran at room temperature leads to Yb( t Budad) 3 ( 1 ), which is also obtained from the reaction of YbCl 3 and three molar equivalents of K( t Budad) in tetrahydrofuran or by metal vapor synthesis. 1 has been characterized by X-ray diffraction. The crystals are monoclinic, space group C 2, Z = 2 with a = 1034.8(9), b = 1710.4(6), c = 1020.4(8) pm, β = 113.28(2)°. The structure was refined to R = 0.0274 for 1466 observed reflections ( F O > 4 σ ( F O )). The structure shows that the empirical composition is Yb( t Budad) 3 and that the coordination number of Yb is six, but the X-ray data are not sufficiently accurate to judge if the oxidation state of ytterbium is zero, two or three. The magnetic susceptibility of solid 1 , prepared by metal vapor synthesis, was studied from 5 to 300 K. The magnetic results are explained by postulating that the bivalent ytterbium species [Yb II ( t Budad)] predominates at low temperature and as the temperature increases the trivalent ytterbium species [Yb III ( t Budad − ) 3 ] predominates in the solid state.

Metallorganische Verbindungen der Lanthanoide. LV: Etherspaltung durch Organolanthanoide: Isolierung und Rontgenstrukturanalyse von [(C5H5)2Lu-(μ-O(CH2)4P(C6H5)2)]2 und [(C5H5)2Lu(OC4H8)]2(μ-O)

Abstract Cp 2 LuCH 2 SiMe 3 (THF) reacts with HPPh 2 and HAsPh 2 to give Cp 2 LuPPh 2 (THF) ( 2 ) and Cp 2 LuAsPh 2 (THF) ( 3 ) respectively. Crystallization of 2 yields [Cp 2 Lu(μ-O(CH 2 ) 4 PPh 2 )] 2 ( 4 ) by THF cleavage, whereas 3 is hydrolyzed to give [Cp 2 Lu(THF)] 2 O ( 5 ).

Organometallic compounds of the lanthanide—XL. Recent developments in organolanthanide chemistry

Abstract Lanthanide trichlorides LnCl3 react with pentamethylcyclopentadienyl alkali metal derivatives with formation of novel compounds of the type C5Me5LnCl3MLn (M = alkali metal, L = donor solvent like Et2O, THF, DME). X-ray structural investigations showed that YbCl3 reacts with KC5Me5 in THF and DME with formation of [K(DME)3][K((C5Me5Yb)3Cl8K(DME)2)2]. Compounds of the type Cp2Ln(μ-CH3)2LiL2 and [Li(TMED)2][CpLn(CH3)3] are useful starting materials for the synthesis of new organolanthanide derivatives with bonds between the lanthanides and other elements. By their reactions with tBuSH, PhSeH, Ph2Ph, and Ph2AsH, e.g. the new organolutetium compounds (C5Me5)2Lu(μ-StBu)2Li(THF)2, (C5H5)2Lu(μ-SePh)2Li(THF)2, (C5H5)2Lu (μ-PPh2)2Li(TMED), and (C5H5)2Lu(μ-AsPh2)2Li(TMED) could be synthesized and characterized by X-ray structural analyses. Dicyclopentadienylsamarium chloride reacts with trimethylsilyl lithium in DME with formation of [Li(DME)3][(C5H5)2Sm(SiMe3)2], whereas in the reaction of (C5H5)2Sm(μ-Cl)2Na(DME) with LiGeMe3 redistribution occurs with formation of hexamethyldigermane and [Li(DME)3][(C5H5)3SmClSm(C5H5)3]. The same anion is formed in the reaction of NaCl with (C5H5)3Sm in DME. Finally LiN3 reacts with (C5H5)3Sm in DME with formation of the complex [Li(DME)3][(C5H5)3SmNNNSm(C5H5)3].

Metallorganische verbindungen der lanthanoide: LVI. Synthese und röntgenstrukturanalyse von [Li(THF)4][(C5H5)2Lu(NPh2)2]☆

Cp2Sm(μ-CH3)2Li(tmed) reacts with HNPh2 to give [Li(tmed)2][Cp2Sm(NPh2)2]. The structure of the corresponding Lu derivative, prepared in tetrahydrofuran, [Li(THF)4][Cp2Lu(NPh2)2] has been determined by an X-ray diffraction study. The crystals are triclinic, space group P1, with a 1418.8(8), b 1512.7(6), c 1301.6(4) pm, α 114.68(3), β 99.85(3), γ 76.55(4)°, Z = 2, R = 0.0746 for 8535 observed data (I ⩾ 6σ(I)).

Organometallic compounds of the lanthanides LII. Synthesis of a new soluble samarium(II) complex containing a ring bridged dicyclopentadiene. Crystal structure of (C5H4CH2CH2CH2C5H4)Yb(THF)2

Abstract (C5H4CH2CH2CH2C5H4)Sm(THF)2 (1) has been obtained as purple crystals by treatment of SmCl2 with Na2(C5H4CH2CH2CH2C5H4) in tetrahydrofuran (THF). The corresponding ytterbium compound 2 results from the analogous reaction using YbCl2 or from the reduction of (C5H4CH2CH2CH2C5H4)YbCl(THF) (3) with Na/Hg in THF. The structure of 2 has been determined by an X-ray diffraction study. The crystals are orthorhombic, space group Fdd2, with a 2938(3), b 3190(7), c 817.8(8) pm, Z = 16, ρcalc. 1.69 g/cm3, R = 0.0454 for 1727 observed data (Fo ⩾ 4σ(Fo)).

Reactions of naphthaleneytterbium with bis(cyclopentadienyl)complexes of cobalt, nickel, chromium and vanadium. X-Ray crystal structure of the triple-decker CpVC10H8VCp

Naphthaleneytterbium, C10H8Yb(THF)3, reacts with Cp2Cr, Cp2Co, Cp2Ni, and Cp2V in THF to give Cp2Yb. In the case of the reaction of C10H8Yb(THF)3 with Cp2V, vanadium-containing intermediates could be isolated. One of them, CpVC10H8VCp, has been characterized by X-ray diffraction. The crystals are monoclinic, space group P21/n, with a 907.0(5), b 798.8(3), c 1080.8(5) pm, β 105.21(4)°; Z = 2. The structure was refined to R = 0.0288 for 1131 observed reflections (Fo > 4σ(Fo)).

Organometallic compounds of the lanthanides XLVI. Synthesis and crystallographic characterization of (C5Me5)2Sm(DME)

Abstract (C5Me5)2Sm(DME) has been obtained as green crystals by the reaction of SmCl2 with NaC5Me5 in dimethoxyethane (DME). Its structure has been determined by an X-ray diffraction study. The crystals are orthorhombic with a 1101.4(4), b 2023.1(5), c 1337.2(5) pm, space group P212121, Z = 4, ϱcalc. 1.34 g cm3, R = 0.0574 and 2524 observed data (I ⩾ 3σ (I)).

Interaction of dicyclopentadienyl chloride complexes of yttrium and lutetium with sodium naphthalenide

The reaction of Cp2LuCl with sodium naphthalenide gives an anionic hydride complex [(Cp2LuH)3H][Na(THF)6] (1) and complex Cp2Lu(2-C10H7)(THF) (2) containing a σ-bonded naphthyl ligand. The structure of1 was confirmed by X-ray analysis. When Cp2YCl is used as the starting material, Cp3Y and an anionic hydride complex also containing a σ-naphthyl ligand are formed. A reaction mechanism involving the formation of an unstable complex [(Cp2Ln+)2(C10H28-)] (4) and its fragmentation into hydride and σ-naphthyl species is proposed.