Synthesis and characterization of new alkoxide and aryloxide deriavatives of titanum and zirconium. X-ray molecular structure

Abstract

Lithium or sodium alkoxides MOR (R = CHzCH=CMez; M = Li 1; Na 2; R = C6F5; M = Li 3) were prepared by reaction of the alcohols with n-butyl lithium or sodium metal in hexane. Reaction of a hexane suspension of 3 with SiCIMe 3 afforded SiMe3(OC6F 5) 4, whereas the reaction of 3 equivalents of C6FsOH with AIMe 3 in hexane led to AI (OC6Fs) Alternative methods can also be followed to synthesize 8 and 11. The crystal and molecular structure of 8 has been determined by X-ray diffraction methods. The most interesting feature of this structure is the disposition of the (C6F 5) ring planes, which are located practically on the reflection plane defined by O(1), Zr(1) and O(1)'.

Synthesis and characterization of tert-butylcyclopentadienyl derivatives of hafnium

“…The trimethylsilyl 1,3-di(tert-butyi)cyclopentadiene reagent was obtained by reaction of 1,3-di(tert-butyl)cyclopentadiene, synthesized as a mixture of different possible isomers, with Lin-Bu and chlorotrimethylsilane [4]. When a hexane solution of complex I was treated with a diethyl ether solution of MgCIMe, in a molar ratio 1: 3.1, an almost quantitative yield of the trimethyl hafnium compound (6).…”

“…LiMe (1.6 M diethyl ether solution), MgCIMe (3 M diethyl ether solution) and HfCi 4 (Aldrich) were purchased and used without further purification. Si(C s H 3-1,3 -t Bu 2)Me.~ [4], MgBz 2 • 2THF [5], LiCH2SiMe 3 [6] and TICp [7] were …”

Synthesis of bis (tert-butyl)cyclopentadienyl derivatives of titanium and zirconium. NMR spectra and dynamic behaviour of the base-free [Zr(1,3-tBu2-η5-C5H3)(CH2Ph)2]+ cation

“…MeLi (1.6 M diethyl ether solution), MeMgC1 (3 M diethyl ether solution), TiCl 4 and ZrCI 4 (Aldrich) were ~urchased and used without further purification. Si(1,3-Bu2-C5H3)Me 3 [9] and MgBz2 2THF [10] were prepared according to published procedures. LiCH 2-CMe2Ph was prepared as a yellow microcrystalline solid by reaction of lithium metal with C1CHzCMezPh (Aldrich) in hexane under reflux for one week.…”

Facile synthesis and X-ray structures of (η5-C5Me5)Ti(OArF)3 (OArF=OC6F5, OCH2C6F5, and OCH2C6F2H3)

“…However, there are only few reports for the polymerization catalysis using nonbridged Cp 0 TiX 3 complexes, which contain both one pentahapto ligand and three monodentate ligands, though the syntheses of these complexes have been known for several decades [3]. The examples include (g 5 -C 5 R 5 )TiCl 3 [4] and (g 5 -C 5 Me 5 )Ti(OR 0 ) 3 (R = H and Me; R 0 = Me, Et, Bu, and so on) [5,6]. Several types of (g 5 -C 5 Me 5 )Ti(OR 0 ) 3 have been synthesized by a two-step reaction in which LiOR 0 is made from R 0 OH and n-BuLi, followed by reaction with a third equivalent of (g 5 -C 5 Me 5 )TiCl 3 [5,6].…”

“…The examples include (g 5 -C 5 R 5 )TiCl 3 [4] and (g 5 -C 5 Me 5 )Ti(OR 0 ) 3 (R = H and Me; R 0 = Me, Et, Bu, and so on) [5,6]. Several types of (g 5 -C 5 Me 5 )Ti(OR 0 ) 3 have been synthesized by a two-step reaction in which LiOR 0 is made from R 0 OH and n-BuLi, followed by reaction with a third equivalent of (g 5 -C 5 Me 5 )TiCl 3 [5,6]. However, yields were somewhat low and some by-product could be obtained.…”