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Synthesis and solid state structures of sterically crowded d0-metallocenes of magnesium, calcium, strontium, barium, samarium, and ytterbium

Version 2 2024-06-05, 00:22
Version 1 2018-09-11, 15:34
journal contribution
posted on 2024-06-05, 00:22 authored by F Weber, H Sitzmann, Madeleine SchultzMadeleine Schultz, CD Sofield, RA Andersen
The base-free metallocenes [1,2,4-(Me3C)3C5H2]2Ca, [1,2,4-(Me3C)3C5H2]2Sr, and [1,2,4-(Me3C)3C5H2]2Ba have been prepared by reaction of MI2and the sodium or potassium salt of the substituted cyclopentadiene anion in THF, while [1,2,4-Me3C)3C5H2]2Mg was prepared from the cyclopentadiene, 1,2,4-(Me3C)3C5H3, and dibutylmagnesium. The structures of the magnesocene and calcocene as well as those of the previously prepared ytterbium and samarium analgoues have been determined by X-ray crystallography. The metallocenes are slightly bent in the solid state with centroid-metal-centroid angles ranging from 163° to 173°. Adducts of the strontocene and samarocene with THF and of the barocene, samarocene, and ytterbocene with 2,6-Me2C6H3NC have also been prepared and characterized. The massive bulk of the [1,2,4-(Me3C)3C5H2]-ligand leads to behavior quite different from that previously observed for base-free metallocenes of the alkaline earths and divalent lanthanides.

History

Journal

Organometallics

Volume

21

Pagination

3139-3146

Location

Washington, D.C.

ISSN

0276-7333

Language

eng

Publication classification

C Journal article, C1.1 Refereed article in a scholarly journal

Copyright notice

2002, American Chemical Society

Issue

15

Publisher

American Chemical Society