Acyl and alkoxy derivatives of dicyclopentadienyltitanium and the refraction increment of the ?-C5H5Ti group

Multicomponent Mechanochemical Synthesis of Cyclopentadienyl Titanium tert-Butoxy Halides, CpxTiXy(OtBu)4–(x+y) (x, y = 1, 2; X = Cl, Br)

“…Its presence may be the result of incomplete alcoholysis, a difficulty that has been observed before with this synthetic method. 46 Nevertheless, both the original and our low-temperature redetermination agree on the pseudotetrahedral nature of the molecule, defined by the centroids of the two Cp rings, the chloride, and the oxygen of the methyl group (Figure 2). The Ti−Cl, Ti−O, and Ti-ring centroid distances in the two structures differ by less than 0.01 Å and the Cl−Ti−O angles differ by only 0.19°.…”

“…Preliminary attempts to prepare Cp 2 TiCl(OMe) 45 ( 1 ) and the previously unknown Cp 2 TiCl(O i Pr) ( 2 ) through grinding Cp 2 TiCl 2 with the appropriate alkali metal alkoxide did not produce clean results, and hence, for these two compounds, we turned to alcoholysis reactions in THF with an added base. 46 This approach has been used with both bis(cyclopentadienyl) 47 and mono(cyclopentadienyl)titanium 26h complexes and provides control over substitution, as indicated in eq 1 ( n = 2 or 3; R = Me, Et, and i Pr) for the latter compounds. 26h For this study, we used Cp 2 TiCl 2 as a starting material, which is inexpensive and its chloride ligands are substitutable.…”

“…These solution reactions are slow (ca. 16 h) and even then may be incomplete, 47 and for the synthesis of the tert -butoxy derivative Cp 2 TiCl(O t Bu) ( 3 ), we investigated halide metathesis instead. This approach has been used to form Cp 2 ZrCl(O t Bu) in THF, 23 although the solution route fails for Cp 2 HfCl(O t Bu).…”

“…The new isoproxy derivative 2 is an orange solid with the expected 1 H and 13 C NMR spectra. The ethoxy derivative has been previously synthesized, , but it was useful for comparative studies (see below) and was also prepared via the literature solution method.…”

Alkinol- und Alkindiol-substituierte Titanocen-Komplexe; Synthese, Reaktionsverhalten und Strukturmerkmale / Alkyne-ol and Alkyne-diol Substituted Titanocene Complexes; Synthesis, Reaction Behaviour and Structural Features

“…Titanocendichloride reagieren mit protonen aktiven Molekülen wie Alkoholen [1][2][3][4], C arbon säuren [5,6] in Gegenwart von N E t3 zu Verbin dungen der A rt Cp2Ti(Cl)2_"(OR)" (n = 1,2) bzw. CpTi(Cl)3_"(OR)" (n = 1, 2) (R = einbindiger or ganischer Rest; Cp = ?/5-C5H 5) [1][2][3][4][5][6] …”