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Cyclononatetraenyl‐Indenyl Transformation and a Zirconium(III) Trimer from Bulky Alkylcyclopentadienylzirconium Chlorides
Author(s) -
Schäfer Sebastian,
Bauer Heiko,
Becker Julia,
Sun Yu,
Sitzmann Helmut
Publication year - 2013
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/ejic.201300885
Subject(s) - chemistry , zirconium , trimer , cyclopentadienyl complex , monomer , medicinal chemistry , metallocene , molecule , crystallography , dimer , inorganic chemistry , stereochemistry , polymerization , organic chemistry , catalysis , polymer
Structure determinations of the known titanium, zirconium, and hafnium trichloro‐di( tert ‐butyl)cyclopentadienyl complexes [Cp″MCl 3 ] {Cp″ = η 5 ‐C 5 H 3 t Bu 2 , M = Zr ( 2 ), Ti ( 3 ), Hf ( 4 )} on crystals obtained by sublimation show monomeric molecules in the solid state. Unlike the racemic di( tert ‐butyl)(trimethylsilyl)cyclopentadienylzirconium trichloride 5 , the 2,3‐diisopropyl‐1,4‐dimethylcyclopentadienylzirconium trichloride 7 is not a monomer according to its low volatility and the presence of two similar sets of signals in the NMR spectra. Reactions of 2 or its Cp″′ analogue [(η 5 ‐C 5 H 2 t Bu 3 ‐1,2,4)ZrCl 3 ] ( 1 ) with potassium cyclononatetraenide did not afford the desired cyclononatetraenyl complexes [Cp″′ (C 9 H 9 )ZrCl 2 ] or its Cp″ analogue, but the indenyl complexes [Cp″′(C 9 H 7 )ZrCl 2 ] ( 8 ) and [Cp″(C 9 H 7 )ZrCl 2 ] ( 9 ). By reduction of the starting compound 1 with potassium a dark red, paramagnetic zirconium(III) complex was obtained and characterized as the cyclic trimer 10 with almost equal Zr ··· Zr distances of 3.384 Å.