Syntheses and Molecular Structures of [(thf)4Li] [{(thf)Li}M(C4H8)3] (M = Zr,Hf) and Their Solution Behavior |
| |
| Authors: | Reinald Fischer Heiner Schmidt Fadi M Younis Helmar Görls Regina Suxdorf Matthias Westerhausen |
| |
| Institution: | Chair of Inorganic Chemistry I, Friedrich-Schiller-University Jena, Humboldtstr. 8, 07743 Jena, Germany |
| |
| Abstract: | The reaction of MCl4(thf)2 (M = Zr, Hf) with 1,4-dilitiobutane in diethyl ether at –25 °C or at 0 °C with a molar ratio of 1 : 3 yields the homoleptic “ate” complexes (thf)4Li] {(thf)Li}M(C4H8)3] 1 - Zr (M = Zr) and 1 - Hf (M = Hf). The crystalline compounds form ion lattices with solvent-separated (thf)4Li]+ cations and {(thf)Li}M(C4H8)3]– anions. The NMR spectra at –20 °C show magnetic equivalence of the M–CH2 and of the β-CH2 groups of the butane-1,4-diide ligands on the NMR time scale. Analogous reactions of MCl4(thf)2 with 1,4-dilithiobutane with a molar ratio of 1 : 2 proceed unclear. However, single crystals of Li(thf)4] HfCl5(thf)] ( 2 ) can be isolated with the hafnium atom in a distorted octahedral coordination sphere of five chloro and one thf ligand. NMR spectra allow to elucidate the time-dependent degradation of 1-Hf and 1-Zr in THF and toluene at 25 °C via THF cleavage. Addition of tmeda to a solution of 1-Zr allows the isolation of intermediately formed {(tmeda)Li}2Zr(nBu)2(C4H8)2] ( 3 ). |
| |
| Keywords: | Zirconium Hafnium Organohafniate complexes Organozirconiate complexes α ω-Alkanediides |
|
|
