Ilse Albrecht

Organometallic compounds of the lanthanides

Abstract Bis(tetrahydrofuran)lithium dimethylbis(cyclopentadienyl)lutetate( III ) have been shown to react with t-butyl alcohol, t-butyl hydrosulfide, and phenyl hydroselenide in ether at −78°C to give the complexes (C 5 H 5 ) 2 Lu(OC 4 H 9 -t)(THF), (C 5 H 5 ) 2 Lu(SC 4 H 9 -t) 2 Li(THF) 2 , and (C 5 H 5 ) 2 Lu(SeC 6 H 5 ) 2 Li(THF) 2 , respectively. The analogous pentamethylcyclopentadienyl complexes (C 5 Me 5 ) 2 Lu(OC 4 H 9 -t)(THF), and (C 5 Me 5 ) 2 Lu(SC 4 H 9 -t) 2 Li(THF) 2 have been prepared from (C 5 Me 5 ) 2 Lu(μ- CH 3 ) 2 Li(THF) 2 and t-C 4 H 9 OH or t-C 4 H 9 SH, respectively. The new compounds have been characterized by elemental analysis and 1 H and 13 C NMR spectroscopy. The structures of the complexes (C 5 Me 5 ) 2 Lu(SC 4 H 9 -t) 2 Li(THF) 2 ( 7 ) and (C 5 H 5 ) 2 Lu(SeC 6 H 5 ) 2 Li(THF) 2 ( 8 ) have been determined by X-ray diffraction. The crystals of 7 are monoclinic with a 19.016(7), b 17.206(6), c 11.899(4) A, β 101.82(3), space group P 2 1 / n , Z = 4, R = 0.052, and 4228 observed ( I >- 2σ( I )) reflections. The crystals of 8 are monoclinic with a 21.60( 3 ), b 13.98(1), c 11.43(1) A, β 120.68(7)°, space group P 2 1 / a , Z = 4, R = 0.066, and 2615 observed ( I >- 3σ( I )) reflections.

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].

Some novel halide- and alkyl-derivatives of pentamethylcyclopentadienyllanthanum, -praseodymium, -ytterbium and -lutetium

Abstract LaCl 3 and PrCl 3 react with NaC 5 Me 5 or KC 5 Me 5 in tetrahydrofuran in the presence of ether or dimethoxyethane (dme) to form the new complexes (C 5 Me 5 ) 2 La(μ-Cl) 2 K(L 2 ), (C 5 Me 5 ) 2 Pr(μ-Cl) 2 Na(L 2 ) (L = Et 2 O, dme) and, C 5 Me 5 PrCl 3 Na(Et 2 O). These compounds react with LiCH 3 or LiCH 2 SiMe 3 forming new alkyl derivatives of the type (C 5 Me 5 ) 2 Ln(μCH 3 ) 2 Li(tmed) (Ln = La, Lu, tmed = tetramethylethylenediamine), [Li(dme) 3 ] [(C 5 Me 5 ) 2 Lu(CH 2 SiMe 3 ) 2 ] and [Li(tmed) 2 ] [C 5 Me 5 Ln(CH 3 ) 3 ] (Ln = Yb, Lu). The structure of (C 5 Me 5 ) 2 Pr(μ-Cl) 2 Na(dme) 2 was determined by X-ray diffraction.

Metallorganische Verbindungen der Lanthanoide. XXIII: Synthese und Struktur von [Li(tmed)2][C5Me5Lu(CH3)3]

Abstract LaCl 3 , YbCl 3 and LuCl 3 react with NaC 5 Me 5 and LiCH 3 or LiCH 2 SiMe 3 in tetrahydrofuran in the presence of tetramethylethylenediamine (tmed) under formation of the new complexes (C 5 Me 5 ) 2 Ln(μ-CH 3 ) 2 Li(tmed) (Ln = La, Lu), [Li(dme) 2 ][(C 5 Me 5 ) 2 Lu(CH 2 SiMe 3 ) 2 ] and [Li(tmed) 2 ][C 5 Me 5 Ln(CH 3 ) 3 ] (Ln= Yb, Lu). The structure of [Li(tmed) 2 ][C 5 Me 5 Lu(CH 3 ) 3 ] has been determined by X-ray diffraction.

Metallorganische verbindungen der lanthanoide: XXXVIII. Synthese und charakterisierung von pentamethylcyclopentadienyl(chloro)-dialkyllanthanoid-anionen☆

Zusammenfassung YbCl 3 and LuCl 3 react with NaC 5 Me 5 and LiC(CH 3 ) 3 in tetrahydrofuran in the presence of tetramethylethylenediamine (tmed), with formation of the new complexes [Li(tmed) 2 ][C 5 Me 5 Yb(t-C 4 H 9 ) 2 Cl] and [Li(thf) 3 ][C 5 Me 5 Lu(t-C 4 H 9 ) 2 Cl].