Characterization of Bis[chloridodi(cyclopentadienyl)zirconium] oxide, a compound containing the Zr-O-Zr linkage

Abstract

The previously reported reaction of dichloridodi(cyclopentadienyl)zirconium [(C5H5)2ZrCl2] with aniline or other bases has been shown to involve water as a reactant, with formation of the oxygen-bridged bis[chloridodi(cyclopentadienyl)- zirconium] oxide, [(C5H5),ZrCl]2O, containing the linkage Zr-0-Zr. The compound is diamagnetic, stable to air and water, and can be sublimed in a vacuum at 200-220�. The crystals are monoclinic, with four molecules per unit cell. The structure was established by mass, infrared, near infrared, and proton magnetic resonance spectral examination, and by reaction of the compound with deuterium-labelled and tritium-labelled hydrogen chloride to regenerate unlabelled dichloridodi(cyclopentadienyl)-zirconium.

ansa-metallocene derivatives

“…The zirconocene derivatives (C5H5hZrCI2 [11], (C 5 (CH 3 )5hZrCI 2 [12] and C2H4(C5(CH3)4hZrCI2 [10] were prepared by published methods. (C 5 -(CH3)5hZrCl2 and C2H4(C5(CH3)4hzrCI2 were converted into their difluoride and dibromide analogues by methods reported for the corresponding permethyltitanocene dihalides [13].…”

Bis(chlorocyclopentadienylzirconium)oxide

“…[(n-CsHs)2ZrCI]zO was prepared as described by Reid, Shannon, Swan & Wailes (1965). Crystals were obtained by sublimation at 200°C under vacuum.…”

Stoicheiometric reduction of CO and CO2to methanol: evidence for carbon monoxide insertion into zirconium–hydrogen bond

“…Attempts to obtain suitable crystals for an X-ray analysis were unsuccessful. The following products were obtained, in almost quantitative yields, when (11) From the results outlined above, it is possible to conclude that the CH,O group is C-and 0-bonded to two different zirconium atoms. The molecular ion was not observed in the mass spectrum of (11), but the peak a t m/e 470 is probably due to the fragment [(cp,Zr),CH,O]+.…”

“…A much slower absorption of CO by (11) is observed, but this does not affect the first fast step. Compound (11) analysed correctly for the proposed formula and is monomeric in benzene, M 590 (calc. 543).…”