10.1021/acs.organomet.5b00303.s001
Kotohiro Nomura
Kotohiro
Nomura
Udomchai Tewasekson
Udomchai
Tewasekson
Yuki Takii
Yuki
Takii
Synthesis of Titanium Complexes Containing an Amine Triphenolate Ligand of
the Type [TiX{(O-2,4‑R<sub>2</sub>C<sub>6</sub>H<sub>2</sub>)‑6-CH<sub>2</sub>}<sub>3</sub>N] and the Ti–Al Heterobimetallic
Complexes with AlMe<sub>3</sub>: Effect of a Terminal Donor Ligand
in Ethylene Polymerization
American Chemical Society
2015
Ethylene PolymerizationThe synthesis
Terminal Donor Ligand
OC
MAO
OCH
terminal donor ligand
Amine Triphenolate Ligand
CH
AlMe 3
Titanium Complexes Containing
TiX
tBu
complex
heterobimetallic
2015-07-13 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Synthesis_of_Titanium_Complexes_Containing_an_Amine_Triphenolate_Ligand_of_the_Type_TiX_O_2_4_R_sub_2_sub_C_sub_6_sub_H_sub_2_sub_6_CH_sub_2_sub_sub_3_sub_N_and_the_Ti_Al_Heterobimetallic_Complexes_with_AlMe_sub_3_sub_Effect_of_a_Terminal_Donor_Ligand_in_/2562481
The synthesis of various titanatranes
containing tris(aryloxo)amine
ligands, TiX[{(O-2,4-R<sub>2</sub>C<sub>6</sub>H<sub>2</sub>)-6-CH<sub>2</sub>}<sub>3</sub>N] [R = Me (<b>1</b>), <sup><i>t</i></sup>Bu (<b>2</b>); X = O<sup><i>i</i></sup>Pr (<b>a</b>), O<sup><i>t</i></sup>Bu (<b>b</b>), OCH(CF<sub>3</sub>)<sub>2</sub> (<b>c</b>), OC(CF<sub>3</sub>)<sub>3</sub> (<b>d</b>), Cl (<b>e</b>)], and some reactions with
Al alkyls have been explored. The Ti–Al heterobimetallic complexes
[TiMe{(O-2,4-Me<sub>2</sub>C<sub>6</sub>H<sub>2</sub>-6-CH<sub>2</sub>)<sub>2</sub>(μ<sub>2</sub>-O-2,4-Me<sub>2</sub>-C<sub>6</sub>H<sub>2</sub>-6-CH<sub>2</sub>)}N]-[Me<sub>2</sub>Al(μ<sub>2</sub>-OR′)] [R′ = <sup><i>t</i></sup>Bu
(<b>3b</b>), CH(CF<sub>3</sub>)<sub>2</sub> (<b>3c</b>), C(CF<sub>3</sub>)<sub>3</sub> (<b>3d</b>)] were isolated
by reaction of <b>1b</b>–<b>d</b> with 1 equiv
of AlMe<sub>3</sub>, whereas reaction of <b>2b</b> with AlMe<sub>3</sub> in toluene did not take place under the same conditions,
and the reaction of <b>2c</b> afforded the methyl complex TiMe[{(O-2,4-<sup><i>t</i></sup>Bu<sub>2</sub>C<sub>6</sub>H<sub>2</sub>)-6-CH<sub>2</sub>}<sub>3</sub>N]. Structures of <b>3b</b>,<b>c</b> were determined by X-ray crystallography. These complexes exhibited
high catalytic activities for ethylene polymerization in <i>n</i>-octane in the presence of MAO, and the activity by <b>1</b> and <b>2</b> was affected by the terminal donor ligand (X)
as well as the substituent on the atrane ligand (R). The activities
by <b>1c</b>,<b>d</b> increased upon addition of AlMe<sub>3</sub>, and the corresponding heterobimetallic complexes (<b>3c</b>,<b>d</b>) showed high activities, whereas an increase
in the activity upon addition of AlMe<sub>3</sub> was not observed
by <b>1b</b>,<b>e</b>, and <b>2c</b>,<b>e</b>.