UNSPECIFIED (1994) MOLECULAR AND ELECTRONIC-STRUCTURES OF BIS[1,4-BIS(TRIMETHYL-SILYL)CYCLOOCTATETRAENE] SANDWICH COMPLEXES OF TITANIUM AND ZIRCONIUM. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS (19). pp. 2867-2874. ISSN 0300-9246

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Abstract

The reaction between 2 equivalents of [Li2{C8H6(SiMe3)2}] and [MCl4(thf)2] (M = Ti or Zr) in tetrahydrofuran (thf) afforded the sandwich complexes [M{C8H6(SiMe3)2}2]. X-Ray studies showed that the zirconium compound adopts a structure in which one ring is bound in an eta8 fashion whilst the other adopts a novel eta3 co-ordination mode. This unusual bonding situation has been studied using extended-Huckel molecular-orbital calculations and photoelectron spectroscopy. In contrast, the titanium compound adopts a solid-state structure in which one ring is eta8 bound and the other is less readily classified, being intermediate between the eta3 structure found for Zr and the eta4 structure found in [Ti(C8H8)2]. Variable-temperature solution NMR studies on [M{C8H6(SiMe3)2}2] showed that the two rings remain indistinguishable even at 193 K for M = Zr, whereas for M = Ti the two rings only become equivalent on the NMR time-scale above 328 K.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
Publisher:	ROYAL SOC CHEMISTRY
ISSN:	0300-9246
Date:	7 October 1994
Number:	19
Number of Pages:	8
Page Range:	pp. 2867-2874
Publication Status:	Published
URI:	http://wrap.warwick.ac.uk/id/eprint/20257

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