Stepwise Modification of Titanium Alkoxy Chloride Compounds by Pyridine Carbinol

Abstract

The stepwise modifications of stoichiometric mixtures of titanium chloride (TiCl 4) and titanium iso-propoxide (Ti(OPr (i)) 4) by 2-pyridine methanol (H-OPy) led to the isolation of a systematically varied, novel family of compounds. The 3:1 reaction mixture of Ti(OPr (i)) 4:TiCl 4 yielded [Cl(OPr (i)) 2Ti(mu-OPr (i))] 2 ( 1). Modification of 1 with 1 and 2 equiv of H-OPy produced [Cl(OPr (i)) 2Ti(mu c-OPy)] 2 ( 2, where mu c = chelating bridge) and "(OPy) 2TiCl(OPr (i))" ( 3, not crystallographically characterized), respectively. Altering the Ti(OPr (i)) 4 to TiCl 4 stoichiometry to 1:1 led to isolation and identification of another dimeric species [Cl 2(OPr (i))Ti(mu-OPr (i))] 2 ( 4). Upon modification with 1 equiv of H-OPy, [Cl 2(OPr (i))Ti(mu c-OPy)] 2 ( 5) was isolated from toluene and (OPy)TiCl 2(OPr (i))(py) ( 6) from py. An additional equivalent of H-OPy led to the monomeric species (OPy) 2TiCl 2 ( 7). Because of the low solubility and similarity in constructs of these compounds, additional analytical data, such as the beryllium dome or BeD-XRD powder analyses, were used to verify the bulk samples, which were found to be in agreement with the single crystal structures.

Tris(2,6‐diisopropylphenolato)titanium(IV) Dihydridodiorganylborates: Synthesis and Structures

“…In general, compounds of the type (RO) 4 Ti are monomeric, for example, (2,6-iPrC 6 H 3 O) 4 Ti, [18] (2-tBu-C 6 H 4 O)Ti, [9] (2,3,5,6-Me 4 C 6 HO) 4 Ti [9] and[2,6-Me 2 C 6 H 3 O] 4 -Ti. [29,30] This also holds for several other triorganylphenolatotitanium(IV) compounds, for example, (2,4-tBu 2 C 6 H 3 O) 3 -TiCl, [10] (3,5-tBu 2 C 6 H 3 O) 3 TiI, [31] tris(2,4-tBu 2 C 6 H 4 O) 3 TiCl, [10] (2-PhC 6 H 4 CO) 3 TiCl · OEt 2 [10] and (2,6-Ph 2 C 6 H 3 O) 3 -TiCl. [14] In contrast, (iPr 2 C 6 H 3 O) 3 TiCl is dimeric, [31] as is (2,4-Me 2 C 6 H 3 O) 3 TiCl.…”

“…[29,30] This also holds for several other triorganylphenolatotitanium(IV) compounds, for example, (2,4-tBu 2 C 6 H 3 O) 3 -TiCl, [10] (3,5-tBu 2 C 6 H 3 O) 3 TiI, [31] tris(2,4-tBu 2 C 6 H 4 O) 3 TiCl, [10] (2-PhC 6 H 4 CO) 3 TiCl · OEt 2 [10] and (2,6-Ph 2 C 6 H 3 O) 3 -TiCl. [14] In contrast, (iPr 2 C 6 H 3 O) 3 TiCl is dimeric, [31] as is (2,4-Me 2 C 6 H 3 O) 3 TiCl. [10] Amongst these species (2,4-tBu 2 -C 6 H 3 O)TiCl shows the shortest Ti-O bond with 1.575 Å, whereas the longest Ti-O bonds were determined for (3,5-tBu 2 C 6 H 3 O) 3 TiI.…”

Structural characterization of methanol substituted lanthanum halides

“…[20, 75, 76] The BeD-XRD patterns were obtained for 4 – 7 (Figure 8) and were compared to the simulated powder X-ray patterns generated from the solved single crystal structure. The patterns obtained for 6 (Figure 8a) were found to be consistent with the theoretical patterns.…”

“…Information pertaining to the details of the beryllium dome XRD (BeD-XRD) analyses has been previously disseminated;[20, 75, 76] hence, only a short description is presented here. All sample preparation was performed in an argon filled glovebox using a 1 cm quartz disk (zero-background plate), where the sample was pressed into the specimen cavity, leveled to the holder base using a glass slide, and the BeD cover sealed.…”

Cytotoxic activity of the titanium alkoxide (OPy)2Ti(4AP)2 against cancer colony forming cells

“…A series of novel organotitanium compounds were synthesized as previously described [10, 11]. These compounds were tested for cytotoxic activity in cancer cell lines, wherein (OPy) 2 Ti(4AP) 2 was found to possess significant activity, which is reported here.…”