Cyclononatetraenyl‐Indenyl Transformation and a Zirconium(III) Trimer from Bulky Alkylcyclopentadienylzirconium Chlorides1. Issue 33 (2nd October 2013)

• Record Type: Journal Article
• Authors: Schäfer, Sebastian; Bauer, Heiko; Becker, Julia; Sun, Yu; Sitzmann, Helmut
• Is Part Of: European journal of inorganic chemistry. Issue 33(2013)
• Page Start: 5694
• Page End: 5700
• Publication Date: 2013-10-02
• Subjects: Sandwich complexes -- Trinuclear complexes -- Titanium -- Zirconium -- Hafnium -- Cyclopentadienyl ligands; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201300885
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Structure determinations of the known titanium, zirconium, and hafnium trichloro‐di( tert ‐butyl)cyclopentadienyl complexes [Cp″MCl3 ] {Cp″ = η 5 ‐C5 H3 t Bu2, 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 trichloride5, the 2, 3‐diisopropyl‐1, 4‐dimethylcyclopentadienylzirconium trichloride7 is not a monomer according to its low volatility and the presence of two similar sets of signals in the NMR spectra. Reactions of2 or its Cp″′ analogue [(η 5 ‐C5 H2 t Bu3 ‐1, 2, 4)ZrCl3 ] (1 ) with potassium cyclononatetraenide did not afford the desired cyclononatetraenyl complexes [Cp″′ (C9 H9 )ZrCl2 ] or its Cp″ analogue, but the indenyl complexes [Cp″′(C9 H7 )ZrCl2 ] (8 ) and [Cp″(C9 H7 )ZrCl2 ] (9 ). By reduction of the starting compound1 with potassium a dark red, paramagnetic zirconium(III) complex was obtained and characterized as the cyclic trimer10 with almost equal Zr··· Zr distances of 3.384 Å. Abstract : During a search for cyclononatetraenylzirconium complexes, cyclononatetraenide lost two hydrogen atoms and formed indenyl complexes with alkylcyclopentadienylzirconium(IV) trichlorides. Another starting compound was obtained by potassium reduction of [Cp″′ZrCl3 ]. The trimer [Cp″′ZrCl2 ]3 shows bonding Zr··· Zr interactions of 3.384 Å.