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Coordination Modes of 2,5‐Di( tert ‐butyl)pyrrolide – Crystal Structures of HPyr*, Pyr*H·thf, (thf) 2 LiPyr*, and [(Me 3 Si) 3 C‐Zn] 2 (μ‐Cl)(μ‐Pyr*) (Pyr* = 2,5‐ t Bu 2 NC 4 H 2 )
Author(s) -
Westerhausen Matthias,
Wieneke Michael,
Nöth Heinrich,
Seifert Thomas,
Pfitzner Arno,
Schwarz Wolfgang,
Schwarz Oliver,
Weidlein Johann
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199808)1998:8<1175::aid-ejic1175>3.0.co;2-b
Subject(s) - chemistry , tetrahydrofuran , medicinal chemistry , trimethylsilyl , bond length , substituent , adduct , zinc , ligand (biochemistry) , pincer ligand , crystallography , crystal structure , organic chemistry , catalysis , pincer movement , biochemistry , receptor , solvent
The lithiation of 2,5‐di( tert ‐butyl)pyrrole ( 1 ) yields bis(tetrahydrofuran)lithium 2,5‐di( tert ‐butyl)pyrrolide ( 2 ), which is monomeric in solution as well as in the solid state. Due to the coordination number of three for the lithium atom, short Li–O and Li–N bond lengths of 193 pm are observed. The metathesis reaction of 2 with tris(trimethylsilyl)‐methylzinc chloride ( 3 ) gives colorless bis[tris(trimethyl‐silyl)methylzinc] chloride 2,5‐di( tert ‐butyl)pyrrolide ( 4 ). The pyrrolide ligand and the chlorine atom bridge the zinc atoms. One of the zinc atoms is bonded to the nitrogen atom of the pyrrolide substituent, while the other bonds to the opposite C–C bond. At 215 pm, the Zn–N bond is very long compared to those in alkylzinc amides, whereas the Zn–C distances lie in the range of Zn–C bond lengths found between zinc and η 5 ‐bonded cyclopentadienide ligands. The molecular structures of 1 and of the low‐melting THF adduct 1 ·thf show a similar 2,5‐di( tert ‐butyl)pyrrole molecule, but in the latter case a weak N–H···O bond is observed (N–H 97 pm, O···H 199 pm).