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Visiting the Limits between a Highly Strained 1‐Zirconacyclobuta‐2,3‐diene and Chemically Robust Dizirconacyclooctatetraene
Author(s) -
Reiß Fabian,
Reiß Melanie,
Spannenberg Anke,
Jiao Haijun,
Baumann Wolfgang,
Arndt Perdita,
Rosenthal Uwe,
Beweries Torsten
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201800465
Subject(s) - allene , diene , reactivity (psychology) , chemistry , cyclopentadienyl complex , yield (engineering) , acetone , medicinal chemistry , stereochemistry , organic chemistry , materials science , catalysis , medicine , natural rubber , alternative medicine , pathology , metallurgy
Abstract The reaction of the allene precursor Li 2 (Me 3 SiC 3 SiMe 3 ) with [Cp 2 ZrCl 2 ] (Cp=cyclopentadienyl) was examined. The selective formation of hitherto unknown linear, allene‐bridged dizirconocene complexes [(Cp 2 ZrCl) 2 {−μ‐(Me 3 Si)C 3 (SiMe 3 )−}] and [(Cp 2 Zr) 2 {−μ‐(Me 3 Si)C 3 (SiMe 3 )−} 2 ] was observed. Upon σ coordination of the allenediyl unit to {Cp 2 Zr}, pyrophoric Li 2 (Me 3 SiC 3 SiMe 3 ) is tamed stepwise to yield a surprisingly robust 1,5‐dizirconacyclooctatetra‐2,3,6,7‐ene with cumulated double bonds. This complex is unexpectedly inert against moisture, air, water and acetone. Surprisingly, it degrades under MS conditions to give the highly strained 1‐zirconacyclobuta‐2,3‐diene. All compounds isolated have been fully characterised and the molecular structures are discussed. The stability and reactivity of these complexes are rationalised by DFT computations.